EPA-R2-73-167
                     Environmental Protection Technology Series
Biological Removal of
Carbon  and Nitrogen Compounds
from Coke Plant Wastes
                               Office of Research and Monitoring
                               U.S. Environmental Protection Agency
                               Washington, D.C. 20460

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            RESEARCH REPORTING SERIES
Research reports of the  Office  of  Research  and
Monitoring,  Environmental Protection Agency, have
been grouped into five series.  These  five  broad
categories  were established to facilitate further
development  and  application   of   environmental
technology.   Elimination  of traditional grouping
was  consciously  planned  to  foster   technology
transfer   and  a  maximum  interface  in  related
fields.  The five series are:

   1.  Environmental Health Effects Research
   2.  Environmental Protection Technology
   3.  Ecological Research
   4.  Environmental Monitoring
   5.  Socioeconomic Environmental Studies

This report has been assigned to the ENVIRONMENTAL
PROTECTION   TECHNOLOGY   series.    This   series
describes   research   performed  to  develop  and
demonstrate   instrumentation,    equipment    and
methodology  to  repair  or  prevent environmental
degradation from point and  non-point  sources  of
pollution.  This work provides the new or improved
technology  required for the control and treatment
of pollution sources to meet environmental quality
standards.

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                                               EPA-R2-73-167
                                               April  1973
         BIOLOGICAL REMOVAL OF CARBON AND

    NITROGEN COMPOUNDS  FROM COKE PLANT  WASTES
                         By

                  John  E.  Barker
                  R. J.  Thompson
                 Project  12010 EDY
                  Project  Officer

                   Leon  H.  Myers
   Petroleum-Organic Chemicals Wastes  Section
     Treatment and Control Research Program
Robert  S.  Kerr Environmental Research  Laboratory
                Ada, Oklahoma 74820
                   Prepared for

         OFFICE OF RESEARCH AND MONITORING
      U.S.  ENVIRONMENTAL PROTECTION AGENCY
              WASHINGTON, D.C. 20460
  For sale by the Superintendent o^ DSoettSaeats'j W.S. Government Printing Office, Washington, D.C. 20402
                Price &9$ flptticsttaWtpaid or $2.00 GPO Bookstore

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                       EPA  REVIEW NOTICE
This report has been reviewed by the Environmental Protection Agency
and approved for publication.~ Approval does not,signify that the
contents necessarily reflect the views and policies of the-Environ-
mental Protection Agency^ nor does mention of trade or?commercial
products constitute endorsement or recommendation for use.
                                  ii

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                             ABSTRACT
A one-year study of a biological process for treatment of coke plant
ammonia liquor was conducted.  The process was designed to remove carbon
compounds and ammonia.  The pilot plant consisted of three treatment
systems arranged in series.  These systems were designed for the removal
of carbon compounds, the oxidation of ammonia to nitrate (nitrification),
and the reduction of nitrate to nitrogen gas (denitrification).  The
study was jointly sponsored by the American Iron and Steel Institute,
the Environmental Protection Agency, and Armco Steel Corporation.

The results of the study indicate that the biological process can be
used to remove carbon compounds and ammonia from dilute ammonia liquor.
Treatment efficiencies obtained include removals of greater than 99.9
percent phenol, 80 percent COD and 90 percent ammonia.  Removal efficiencies
for cyanide and thiocyanate were less encouraging with averages of 57
and 17 percent, respectively.  At this time, the inability to efficiently
remove cyanide and thiocyanate raises a question as to the long range
applicability of the process to existing and proposed water quality
standards.                                             ;

A complete evaluation of the capabilities and limitations of the system
was beyond the scope of this study.  Additional development work will be
required before the process could be considered for commercial application.
                                 iii

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                             CONTENTS
Section

    I

   II

  III

   IV
   VI

  VII

 VIII
   IX



    X

   XI

  XII

 XIII

  XIV

   XV
                                                   Page

CONCLUSIONS AND RECOMMENDATIONS                      1

INTRODUCTION                                         5

DESCRIPTION OF PROBLEM                               7

POTENTIAL SOLUTIONS TO PROBLEM                      13
  Modified Method of Coke Production                13
  Quenching                                         14
  Incineration            J                          14
  Distillation                                   14 & 15
  Deep Well Disposal                                15
  Removal or Recovery of Specific Contaminates      15

BIOLOGICAL OXIDATION AND DENITRIFICATION            27
  Biological Oxidation of Coke Plant Wastes         27
  Biological Nitrification and Denitrification      33

DESCRIPTION OF PILOT PLANT                          39

SAMPLING AND ANALYSIS                               45

OPERATIONS AND RESULTS                              49
  The Excess Ammoniacal Liquor                      50
  Carbonaceous Treatment Unit                       52
  Nitrification Unit                                72
  Denitrification Unit                              82

SPECIAL STUDIES                                     91
  Carbonaceous Unit                                 91
  Denitrification Unit                              94

COST ESTIMATES                                      97

ACKNOWLEDGEMENTS                                   103

REFERENCES                                         105

PUBLICATIONS                                       111

GLOSSARY                                           113

APPENDIXES

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                              FIGURES


No.                                                            Page

 1            FLOW DIAGRAM BY-PRODUCT COKE PLANT                 9

 2            HYPOTHETICAL PATHWAYS OF NITRATE REDUCTION        35
              IN MICRO-ORGANISMS

 3            PILOT PLANT FLOW DIAGRAM             .             41

 4            SAMPLING POINT LOCATIONS                          46

 5            CARBON REMOVAL UNIT-PERCENTAGE OF WASTE UNDER     57
              TREATMENT

 6            CARBON REMOVAL UNIT-INFLUENT CONCENTRATIONS,      59
              ORGANIC CARBON AND COD

 7            CARBON REMOVAL UNIT-INFLUENT CONCENTRATIONS,      60
              PHENOLICS

 8            CARBON REMOVAL UNIT-INFLUENT CONCENTRATION,       61
              THIOCYANATE

 9            EXCESS AMMONIA LIQUOR-CONCENTRATIONS, TOTAL       62
              NITROGEN AND AMMONIA
                                  vi

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                              TABLES
No.                                                                 Page

 1          TYPICAL QUANTITIES OF VOLATILE PRODUCTS  PER              8
            ,-TON OF COKE

 2          TYPICAL ANALYSIS OF AMMONIACAL LIQUOR AND  STILL          10
            WASTE

 3          PILOT PLANT EQUIPMENT                                    42

 4          SAMPLING AND ANALYSIS SCHEDULE                           47

 5          EXCESS AMMONIACAL LIQUOR                                 51

 6          SUMMARY OF CHARACTERISTICS - EXCESS AMMONIACAL           52
            LIQUOR

 7          OPERATING CONDITIONS, CARBON REMOVAL UNIT                54

 8          INFLUENT, CARBON REMOVAL UNIT                            55

 9          LOADINGS AND REMOVALS,  CARBON REMOVAL UNIT              56

10          EFFLUENT LOADS PER UNIT VOLUME OF WASTE                  66

11          SUMMARY OF CONDITIONS DURING PERIODS OF  UNIT             70
            STABILITY

12          SUMMARY OF TREATMENT MIT FAILURES                       71

13          OPERATING CONDITIONS, NITRIFICATION UNIT                74

14          NITRIFICATION UNIT, SUMMARY                              77

15          OPERATING CONDITIONS, DENITRIFICATION UNIT              78

16          OPERATING RESULTS, DENITRIFICATION UNIT                  85

17          DENITRIFICATION - STOICHIOMETRIC COMPUTATION             87

18          PRETREATMENT OF EXCESS  AMMONIACAL LIQUOR,                92
            PERCENT REMOVALS

19          BIOLOGICAL REMOVALS FRO?! PRETREATED WASTE                93

20          CAPITA!, COST E.A.L. BIOLOGICAL TREATMENT                98

21          OPERATING COST BIOLOGICAL TREATMENT                     100

22          COST COMPARISONS OF NITRIFICATION CHEMICAL             101
            REQUIREMENTS

23          COST COMPARISON OF ORGANICS FOR DENITRIFICATION         102

                                  vii

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                             SECTION I
                  CONCLUSIONS AND RECOMMENDATIONS
After nearly one year of pilot plant operation, it is concluded that
carbon compounds can be biologically removed from diluted ammonia
liquor.  Although this project demonstrates that ammonia can be
partially removed by biological oxidation, it failed to demonstrate
consistent removal of ammonia to the degree necessary for the
effluent standards, currently under consideration by regularoty
authorities.  The cost per unit of ammonia removal compared to other
processes casts doubt on the commercial feasibility of this aspect of
the process.  Three stages of treatment are required.  These treatment
stages are carbon removal, nitrification and denitrification.  The
three biological processes must be arranged in this order if effective
treatment is to be achieved.

Unanticipated delays and system upsets caused primarily by rapid
fluctuations in ammonia liquor strength prevented the complete evaluation
of important process requirements particularly for the nitrification
system.  Some of the more important parameters not completely defined
are waste loading, temperature, and sludge wasting requirements.  These
parameters have a significant effect on the size, efficiency, and cost
of biological treatment systems.  Additional development to evaluate and
define the effect of these design parameters will be required before the
system could be considered for commercial application.

Several specific observations and conclusions were made during the study.
These are as follows:

     1.  The strength of ammonia liquor is highly variable.  Fluctuations
         by factors of three or more in concentration of many constituents
         were not uncommon.  This variability must be eliminated or
         dampened if stable and efficient biological treatment is to be
         achieved.

     2.  Utilizing an aeration time of 24 hours and temperatures between
         75 and 90°F, the carbonaceous removal unit treated diluted excess
         raw ammonia liquor at influent concentrations of chemical oxygen
         demand of 3000 mg/1 and phenolics of almost 600 mg/1.  Removals
         of essentially all of the phenolics and about three-quarters of
         the COD were experienced.  Operation is improved by the higher
         temperatures.

     3.  Thiocyanate, a major component of ammonia liquor, was only partially
         removed by the carbonaceous removal unit even at very low unit
         loadings.  Apparently, during most of the experiment conditions were
         not conducive to the proliferation of organisms capable of oxidizing
         thiocyanate.  Residual thiocyanate in the carbonaceous units effluent
         is a major contributor to residual COD.

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 4.   Cyanide removal was quite erratic with removal efficiencies
     averaging only 57 percent.  Fluctuations in cyanide removal
     were generally unpredictable and inconsistent with waste
     strength.

 5.   At low unit loadings, significant nitrification of ammonia was
     measured in the carbonaceous treatment stage.

 6.   During one part of the study, the carbonaceous unit efficiently
     removed COD and phenol while operating in a mode similar to an
     aerated lagoon.

 7.   The carbonaceous unit experienced aerator foaming problems which
     increased with increasing waste strength.  Tributyl phosphate
     was an effective control.

 8.   Major problems encountered by the carbonaceous unit included
     variability of loadings resulting from inconsistencies' in the
     raw waste, both high and low reactor temperatures, high reactor
     cyanide and thiocyanate concentrations, and low reactor dissolved
     oxygeii levels.

 9.   Nitrifying organisms are quite sensitive to many constituents in
     ammonia liquor.  Dilution and efficient operation of the carbonaceous
     unit are necessary to prevent inhibition and loss of nitrification
     efficiency.

10.   Nitrification efficiency reached 90 percent oxidation of ammonia
     when the waste was diluted to 12 percent strength and the carbon
     removal unit was operating satisfactorily.
                                                         .,-•
11.   Additions of agents to supply inorganic carbon for metabolism
     of the autotrophic nitrifiers and an alkaline agent to neutralize
     the acidity produced in the process are necessary.  The most
     practical chemical system is sodium carbonate and hydrated lime.

12.   Nitrification was found to proceed satisfactorily x^ithin the pH
     range of 6.8 to 8.2 and that temperatures of 90-95 F were much
     better than 80-85°F.

13.   The maximum observed rate of increase in oxidized nitrogen was
     150 mg/1 of nitrogen per day.  This may give some measure of the
     rate of response of the unit to increases in influent ammonia
     concentration.

14.   The major operational problems of the unit resulted from poor
     quality carbonaceous unit effluent, high nitrification unit pH
     and low nitrification unit temperature.

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    15.  The major biochemical reactions occurring within  the  nitrifi-
         cation unit lead to the oxidation of ammonia  to nitrite  and
         nitrate, the reduction of oxygen, and the reduction of carbon
         dioxide.

    16.  No overall loss of nitrogen took place within the  first  two
         operational units of the pilot plant.

    17.  The denitrification unit was capable of removing 95 to 100
         percent of the oxidized nitrogen at influent  concentrations up
         to 600 ppm.

    18.  Temperature variations between 70 and 90°F had no  observable
         effect on denitrification efficiency.

    19.  Alkalinity and pH control were not necessary  at oxidized nitrogen
         removals up to 600 ppm.

    20.  Sludge bulking in the denitrification unit final clarifier  was
         a problem.  Flotation should be considered for solids separation
         in this system.

    21.  Molasses proved to be an acceptable reducing  agent for denitri-
         fication.  Dean, et^ al_t has suggested methanol as  a reducing
         agent.  From an economic standpoint, methanol which costs twice
         as much as molasses is considered second choice.

    22.  Careful control must be exercised to maintain a reasonable  balance
         between oxidized nitrogen and the reducing agent.  The recommended
         dosage of reducing agent in terms of mg/1 of  chemical oxygen
         demand was found to be equal to about 9 times the  sum of the
         milliequivalents per liter of nitrite and nitrate  to be reduced.

    23.  The complete three-stage treatment plant under optimum operating
         conditions should be capable of removing well over 99 percent of
         the phenolics, 90 percent of the organic carbon, 70 percent of the
         chemical oxygen demand, and 90 percent of the ammonia.

    24.  Preliminary estimates for a treatment system sized for a 33,000
         TPM coke plant are $995,000 capital cost and  $230,500 annual
         operating cost.  The operating cost represents $15.78 per 1,000
         gallons of excess ammonia liquor or $0.58 per net  ton of coke.
         Seventy to eighty percent of this cost is for ammonia removal.
The results of this study strongly suggest that a full-scale biological
system to remove carbon compounds from excess ammonia liquor could be
designed and built.  It also indicates that additional development is
required to enable the construction and operation of a reliable, full-
scale, biological system for removal of the ammonia.

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It is recommended that future research and development efforts be
directed at defining the causes and developing methods to eliminate the
rapid fluctuations in ammonia liquor strength; defining the parameters
required for biological removal of cyanide and thiocyanate, and optimizing
the system for their removal; and evaluating the aerated lagoon as an
alternate to the activated sludge process.

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                            SECTION II
                           INTRODUCTION
The operation of by-product coking facilities results in the discharge
of nutrients, oxygen consuming materials, and toxic substances to the
nation's lakes and streams.  This is one of the major unsolved water
pollution problems facing the steel industry.  The problem is magnified
by the concentration of coke production in small areas of the United
States.  Seventy percent of the producing facilities are located in the
states of Pennsylvania, Indiana, Ohio, and Alabama.  An additional 20
percent are distributed among five northeastern states.  And the
remaining 10 percent are scattered across the country in widely-separated
locations.  The large production of coke, the concentration of coking
facilities, and the increasing requirements for water pollution control
necessitate the development of a practical method for the treatment of
coke plant wastes.  Although a considerable amount of research has been
conducted, the complexity of the wastes has prevented the development of
a practical disposal technique.

Recognizing the need for a practical method for the disposal of coke
plant waste, the American Iron and Steel Institute (AISI) initiated a
laboratory study in 1968 to determine the applicability of biological
treatment to this problem.  The AISI Water Resources Fellowship at
Carnegie-Melion University were responsible for this study.  From the
beginning, it was recognized that several treatment stages would be
required.  These stages would include carbonaceous removal, nitrification,
and denitrification.  The treatment stages were arranged in this order to
prevent inhibition of the nitrifying bacteria by excessive amounts of
organic carbon.  Preliminary results from the laboratory pilot plant study
were quite encouraging with excellent removals of phenol and ammonia.

On the basis of these preliminary laboratory results, it was decided to
conduct a field scale pilot plant study concurrent with the laboratory
study.  The principal objectives of the study were to determine the
technical and economic feasibility of biological treatment of excess
ammoniacal liquor.  In addition, the effect of various controllable
parameters on process efficiency were to be evaluated.

The pilot plant was built at Armco Steel Corporation's Houston, Texas
Works.  At this location, an existing by-products coke plant supplied a
continuous source of waste.  The pilot plant was designed as three
completely mixed activated sludge plants in series with a maximum capacity
of one gallon per minute.  The system started operation in January, 1970
and the study was terminated in January, 1971.  The results of this one
year pilot study including the results of the concurrent laboratory
study are presented in this report.

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                            SECTION III
                      DESCRIPTION OF PROBLEM
Coke is a necessary intermediate product in the manufacture of steel.
The importance of coke in steel production is derived from its strength
as a reducing agent, its physical characteristics, and its low cost.
Coke is used as a reducing agent in the blast furnace where iron ore is
converted to molten iron or "hot metal."  The hot metal is further
refined in open hearth, basic oxygen, or electric furnaces to steel.

The present United States coke production is approximately 60 million
tons annually.  This production is expected to increase essentially at
the same rate as steel production, at least during the next one to two
decades.  At present, more than 98 percent of all United States coke or
59 million tons annually is produced in by-product coke ovens.

The coking operation may be described as a process for the destructive
distillation of coal to produce a coke with satisfactory chemical and
physical properties for use in metallurgical applications.

The by-product coke oven is a long and narrow chamber, built in batteries
usually consisting of 10 to 100 ovens.  The ovens are heated by the com-
bustion of gas evolved from their own charge of coal.  Prior to use, the
gas is thoroughly cleaned and stripped of certain by-products by a series
of cooling and scrubbing operations.  The by-products usually recovered
are gas, tar, ammonia, and light oil.  Many secondary by-products are
obtained from the light oil at separate plants.  The pollution problems
from the production of these secondary products are a considerably
different problem and usually of only minor concern.

The crude gas, e.g., volatile products leaving the ovens is composed of
the permanent gases whose mixture constitute the clean coke oven gas, in
addition to gases or vapors of water, tar, ammonia, phenol, hydrogen
sulfide, hydrogen cyanide, light oil, and naphthalene.  Typical produc-
tion rates of some of these materials are shown in Table 1.  Many of
these materials must be removed from the coke oven gas prior to use in
order to prevent excessive plugging and corrosion of the distribution
system.  It is these gas cleaning and by-product recovery systems that
produce the contaminated waste water.

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                              TABLE 1
      TYPICAL QJJANTmES ^FljyOLATILE J^QgJgTS^XER JTON^OF COKE

      Gas                                         15,000 ft. 3

      Tar                                             10 Sal-

      Light Oil                                        4 8al-

      Ammonia                                          7 lbs-

      Phenolics                                      °-6 lbs-

      Hydrogen Sulfide                                 8 lbs.

      Naphthalene                                    1-5 lbs.
The gas cleaning and by-products recovery system most widely used in the
United States is the semidirect system.   There have been a number of
other systems proposed, some of which have been tried, and at least one
of which, the indirect recovery system,  is in full-scale operation.  The
principal differences between these alternate systems is the method of
ammonia removal and the type of by-product ammonia recovered; i.e.,
ammonium sulfate, diammonium phosphate,  or ammonium hydroxide.  Figure 1
is a flow diagram of the semidirect system.

In the semidirect system the crude gas leaves the ovens through stand-
pipes at the top, which connect to a large collecting main traversing
the full length of the battery.  The gas receives its first cooling in
the collector main by contact with sprays of ammoniacal liquor which was
previously condensed from the gas.  This initial cooling results in the
removal of approximately 85 percent of the tar.  The gas then passes
through the primary cooler where the remaining 15 percent of the tar is
removed.  The primary cooler may be the  direct or indirect type.

From the primary cooler, the gas passes  through the tar extractor, an
electrostatic precipitator, for removal  of the last traces of tar.
Condensate drains are provided at each piece of equipment from the
collector main through the tar extractor.  The condensate is sent to
decanter tanks for separation of the tar.  The recovered tar is used as
fuel in the steel plant or sold to local chemical companies for the
manufacture of a variety of secondary by-products.  The tar-free liquor
is pumped back to the collector main.  Excess amraoniacal liquor resulting
from condensation of gas moisture is sent to an ammonia still.

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TO < FKtoM
RIVER _, -DRIVER
FUUSMIMQ
LIQUOR
:OAL ip^ii , 	 ,
1 1 GAS
fi-JT^
OVENS
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"*• 	 »• ^ GAS »
PRIMARV

t GAS —
FLUSHING TAI*
LIOUOR . SEPARATOR
^ 1
— 1 	 1 TARII

|l
TAR TO STOR
EXCESS
AMMOtllA
LIQUOR
1
1
=j AMMONIA 11
] LIQUOR ||
., ..... 	 t r-"
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*
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RES6R- JiJ| L— ,
VOIR. 1 	 ' II
STEAM 111
AMMONIA
STILL,
STILL,
WASTE
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.E 1 \
r
i
•
t
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— ^^TEB. <%*
II 	 .STORAGE
r^'^ '_» 6Ag| !=5r
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COOLER, SCRURBER BEHTO,
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=IHAL COOLIM<3>
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>R CLEAWOUT

FLOW DIAGRAM To SE'WER
SEMIDIRECT BY-PRODUCT COKE PLANT

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The volume of excess ammoniacal liquor is dependent upon coal moisture
content and varies from 30 to 35 gallons per ton of coke.  This liquor
contains (Table 2) a large percent of the total volatilized ammonia,
nearly all of the phenol, and significant but unrecoverable quantities
of cyanide, thiocyanate, sulfide, and chloride.
                              TABLE 2

       TYPICAL ANALYSIS OF AMMONIACAL LIQUOR AND STILL WASTE

                  Excess *            Undephenolized (1)  Dephenolized  (1)
                  Ammoniacal          Still Waste         Still Waste
                  Liquor	.	  	^	
                  Cone.  Discharge    Cone.  Discharge ,   Cone.  .Discharge
                  (ppm)  Ib./lOOO     (ppm)  Ib./lOOO     (ppm)  Ib./lOOO
                         tons coke    	  tons coke    	  tons coke

Ammonia           3800      1300       155        77       110  ,      50

Phenol            1500       500      1320       725       158        71

Cyanide             20         7
                                                               y.
Thiocyanide        600       200       -

Sulfide              2    '     1       -
                              e

Chloride          7000      2300      4350      2393      5400      2930

Volume
                                                               5>
(gal./ton coke)         33                  55                  45


* Based on analysis from Armco Steel Corporation's Houston Coke Plant
.Ammonia in the excess liquor is volatilized by live steam injection in
the ammonia still.  The volatilized ammonia is reinjected into the gas
stream following the tar extractor.  The gas is then scrubbed with
sulfuric acid in the saturator for removal of ammonia as ammonium
sulfate.

The waste water from the ammonia still is either dephenolized and dis-
charged to a receiving stream or disposed of without dephenolization
usually by evaporation at the quench station.  Two dephenolization
processes are in common use today.  The most modern and efficient
                                  10

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system is the liquid extraction process where benzol or  light oil  is
used to absorb the phenol.  It is later removed  from the absorbent by
caustic extraction to form a sodium phenolate by-product.  The other
dephenolizing system is the vapor recirculation  process  x^here the  phenol
is vaporized with steam.  The steam and phenol vapors are then contacted
with caustic to form sodium phenolate.  Although these processes are
quite efficient, the waste water discharged to the receiving stream still
contains excessive amounts of phenol, ammonia, and cyanide.

Complete elimination of the water waste from the ammonia still can be
accomplished by evaporation at the coke quench station.  Although  this
method is rather widely used, it is an undesirable approach because of
problems with corrosion of the tower, quench car, and local buildings
and equipment.  These problems are a result of the chlorides in the
still_waste.

Following the saturator the gas is cooled in the final cooler in preparation
for light oil removal.  Light oil is scrubbed from the gas by a high
boiling wash oil in the gas scrubber.  The light oil is  then distilled
from the wash oil and the wash oil is recirculated.  The light oil  is
refined in the benzol plant by distillation and  fractiohation into
benzol, toluol, and xylol.  The gas is then ready for distribution.

By-product ammonia recovery from coking operations was a profitable busi-
ness in the early 1900's.  Since that time, an economical process  for
the synthesis of anhydrous ammonia has been developed.   The use of  this
process has resulted in the steadily decreasing  value of ammonium  sulfate
as well as other ammonium compounds.  Today, the cost to produce ammonium
sulfate is higher than its market value and in many locations there is
virtually no market.  In general, by-product ammonia recovery in American
coke plants is no longer considered a profitable venture.  At best  it is
an expensive pollution abatement measure.  For this reason, emphasis on
efficient operation of by-product recovery equipment in  many plants has
been reduced resulting in significant increases  in the discharge of
ammonia, phenol, and other materials as listed in Table  2.  In other
plants, the ammonia recovery equipment has been  completely abandoned
resulting in the direct discharge of ammoniacal  liquor,  and the required
conversion of the final cooler to a once-through system.

The high cost of by-product ammonia recovery, as well as other available
treatment and disposal systems and the inability of these systems  to
produce acceptable effluent quality at many locations, has resulted in
the need for alternative pollution control methods.  It  is the purpose
of this study to evaluate one such alternative—biological treatment.
                                 11

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                            SECTION IV
                  POTENTIAL SOLUTIONS TO PROBLEM
Many mechanisms have been considered to eliminate or reduce  the  amounts
of ammoniacal liquor and for its treatment or disposal.   This  section
will briefly describe some of the treatment or disposal methods  other
than microbiological that have been considered.  Biological  methods will
be reviewed in the succeeding sections.
MODIFIED METHOD OF COKE PRODUCTION

Ammonia liquor itself is an outgrowth of changing technology in the
manufacture of coke.  At one time, the major source of coke in this
country was from beehive ovens.  These devices manufactured coke but no
by-products and used the evolved gases to heat the oven by burning the
gas within the oven itself.  Thus, at no time was the gas allowed to cool
and formation of ammoniacal liquor was avoided.  However, because of air
pollution problems and the desire to recover by-products and the sas
itself, these units were replaced by the currently used slot-type ovens
with  the ammoniacal liquor problem.  Currently, operational changes are
being proposed which may reduce the amount of ammoniacal liquor produced
and new coking techniques are proposed which may eliminate the problem.

One change which may reduce the quantity of ammonia liquor is to predry
the coal prior to charging.  This is a part of a new system being
developed for smokeless charging of slot ovens.  If the vapors evolved
during predrying are not heavily contaminated and do not present a
problem of disposal in themselves, then this would obviously reduce the
quantity of waste.  In addition, this might effect the amounts of other
constituents, especially ammonia.  Ammonia is known to be protected
from  thermal cracking by the presence of such oxygenated compounds as
water.  In fact, at one time, when ammonia was a valuable by-product of
coking, steaming was considered as a method to enhance the yield.  Con-
versely, it might be anticipated that less coal moisture would lead to
reduced amounts of ammonia.

For several years, the coking industry has'been seeking new methods for
making coke.  Currently, several continuous coking processes (2) are
under development.  The major attributes of these processes, according
to their developers, is that they can coke coals that cannot be processed
in the current slot-type ovens and that they reduce air contamination.
No information on potential vrater pollutants is known; and until defini-
tive information is available, the presumption must be made that problems
equal to those in slot-type ovens will exist.  However, it can be hoped
that continuous coking of predryed coal may lead to a lower potential for
water pollution.
                                    13

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QUENCHING

After the coal has been carbonized, the hot coke is removed from  the  oven
and is cooled by direct water sprays.  This process is called quenching.
Coke quenching as presently practiced uses about 500 gallons of water per
ton of coke quenched with a loss of about 150 gallons per ton through
evaporation.  Some coke plants have utilized this evaporative loss to
dispose of ammoniacal liquors as well as other wastes.(1» 3)

A major problem with the use of highly saline waste, such as ammoniacal
liquor for quenching is the increased rate of equipment corrosion.  The
costs incurred from this corrosion are generally high and must be con-
sidered as part of the costs of disposing of ammoniacal liquor.

The concept of coke quenching as a method for the disposal of ammoniacal
liquor was based on the supposition that the potential contaminating
constituents of both air and water were burned by the heat from the coke.
Unfortunately, however, instead of being destroyed, the volatile con-
stituents are simply distilled and discharged to the atmosphere.  This
has been proven in the case of phenolics in one quenching operation (4)
and while not as definitive, some information is available which indi-
cates that sizeable amounts of the ammonia in the quench water is also
released to the atmosphere. (5)  xhe fate of these materials after
release is not known.  In certain instances, this process has been sus-
pected of contributing to air pollution.
INCINERATION

Incineration has been considered as an optimum disposal method for many
kinds of waste products including concentrated liquid wastes.  For
aqueous wastes, in general, the major economic consideration is the dif-
ference between the energy requirements for evaporation of the water and
the energy recovered by combustion of the waste constituents.  In the
case of ammoniacal liquors, an additional problem is encountered.  That
is one of equipment corrosion resulting from the high inorganic chemical
content (especially chlorides) of the waste.  No doubt, incineration of
this waste is technologically possible, but in light of the decreasing
availability and the resultant increasing cost of fossil fuel, the
desirability and the economic feasibility is seriously questioned.
Rudolfs *• ' reports that one installation in Germany evaporates and burns
the residue.  All of the waste water is evaporated directly into the air
by gas-heated furnaces and most of the phenols were burned in the 250-foot
furnace stack.  Increased equipment corrosion is said to result.


DISTILLATION

The major conceptual difference between simple evaporation and distil-
lation is that in distillation the vapors are recondensed while in
evaporation the vapors are usually discharged directly to the atmosphere.

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The equipment is generally much more complex for distillation than for
evaporation but distillation lends itself better to both thermal and by-
product recovery.  Distillation, as a method for treating coke plant wastes,
is not new and is currently the method of choice at many plants for removal
of ammonia and phenolics from ammoniacal liquors.  These specific processes
will be covered later in this section.
One proposed process     ^s stated to treat completely a conventionally free
ammonia distilled and dephenolized liquor by a modified distillation process.
The liquor is distilled to a dry powder after addition of acid to retain the
ammonia and activated carbon to retain the phenolics in the residue.  The
process appears to be fairly complex and no actual applications of the pro-
cess are known.
         i                                              .           ..
The use  of deep injection wells for the disposal of wastewaters has grown
rapidly  in recent years.  The advantages of this method of disposal as
delineated by its proponents include:  (1) complete disposal of waste;
(2) minimum pretreatment needed;  (3) no complicated equipment required; and
(4) low  operating cost.  For coke plants located in a suitable injection
area, disposal of ammonia liquor to a deep well is possible.  Care would
be required in the ,; pretreatment step to assure the complete removal of tars
and other suspended materials that might clog the aquifer.  The compatibility
of waste with the aquifer also needs to be carefully evaluated because of the
many potential reacting chemical species involved.  Two wells are known to
be in operation for disposal of ammoniacal liquor.  One of these wells is
operated by Ford Motor Company in Detroit, Michigan, and the other is
operated by Bethlehem Steel in Indiana.

Currently the use of injection is being reviewed from both a technological
and legal framework and the future use of this process is being seriously
questioned.


REMOVAL  OR RECOVERY OF SPECIFIC CONTAI'IINATES

Most wastes are treated by methods which selectively remove specific con-
taminating substances which prepares the waste adequately for disposal,
reuse, or further treatment.  The contaminates of major concern in coke
plant wastes are divided into two major categories; e.g., carbonaceous and
nitrogenous compounds.  The carbonaceous constituents of major concern have
been phenolic in nature and much of the work has been directed toward the
removal  of this group of compounds.  However, in certain instances, the
removal  of a broader variety of carbonaceous constituents is necessary and
more general methods have been developed.  The Nitrogenous constituent of
major concern has been ammonia.  The discharge of excessive amounts of
ammonia  to receiving waters can interfere with established beneficial uses
for that water.  Among the problems that have on occasion been attributed
to ammonia are fish kills, stimulation of algae growth, interference with
water disinfection, receiving stream oxygen deficiencies, and corrosion of
copper pipes.  Several somewhat specific methods of treatment have been
developed for these constituents and the major ones of these will be re-
viewed briefly in the succeeding paragraphs.
                                   15

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Dephenoli zatipn

Dephenolizatlon (D or removal of phenolics from ammonia liquor for recovery
purposes is widely practiced in this country.  The two major methods in
use are liquid extraction and vapor phase recirculation.  In liquid extrac-
tion, a solvent is used to extract the phenolics from the ammoniacal liquor
prior to ammonia distillation.  A substantial part of the phenol is removed
from the solvent by distillation or by extraction with strong caustic soda.
The latter is preferred in this country.  In the vapor recirculation process,
water vapor is recirculated upward through a tower having two or three sec-
tions in series.  The vapor first passes through one or two caustic soda
scrubbing sections where it is freed of phenols, then on up the tower through
the hot ammoniacal liquor from the free leg of the ammonia still.  The vapor
removes most of the phenols that remain in the liquor, then passes through a
duct and blower to reenter the caustic soda section of the cycle.  Neither
system can be expected to remove more than 95-98 percent of the phenolics.
The resulting dephenolized liquor may not be suitable for discharge in all
instances.
 Chemical Oxidation^of Phenol

 An excellent report  (8) on the results of laboratory and pilot plant experi-
 ments has been prepared for the Ohio River Valley Water Sanitation Commis-
 sion.  This study on the oxidation of dephenolized ammoniacal liquors used
 chlorine, ozone, and chlorine dioxide.  The wastewater treated contained
 from 30 to 300 mg/1 phenolics, 300 to 400 mg/1 of 5-day biochemical oxygen
 demand, and oxygen consumed (dichromate method) values of 1400 to 1800 mg/1.
 Removals of 60 percent of the BOD and OC were reported.  Data shows that
 any of the oxidants tested could be used to remove phenolics.  Approximately
 the following amounts of oxidant were required per mg/1 of phenol to remove
 90 percent of the phenolics when starting at levels above 100 mg/1:  30 mg/1
 for chlorine; 10 mg/1 for chlorine dioxide; and, 4 mg/1 for ozone.  The
 major problem with chlorine was the apparent necessity to satisfy the ammonia
 demand prior to any oxidation of phenol.


 Absorption of Organics

 The removal of organic constituents in ammoniacal liquors by absorption on
 activated carbon was used in Germany in 1930.(9)  in this plant, clarified
 carbonization wastewaters (coke filtered) was passed through beds of activated
 carbon.  Effluent phenol concentrations down to 50 mg/1 were reported.
 Other organics were also removed.  When the activated carbon had taken up 6
 to 10 percent by weight of phenolics, it was washed with benzene to remove
 phenolics and regenerated with steam.  The phenolics were recovered by
 distilling the benzene.  This plant apparently did not operate very long
 because of a drop in the price of phenol.  A possible problem given in the
 cited reference concerns reactivation difficulties resulting from high boiling
 acidic and tarry constituents.  Blackburn (10) and Ackeroyd (11) refer to
 operational plants using activated carbon in England.  Regeneration is again
with benzene and problems with tars have been reported.  The Pittsburgh Coke
and Chemical Company is reported (D to have conducted a series of tests
prior to 1950 using activated carbon but problems with regeneration were
experienced.
                                    16

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Currently a renewed interest has been shown in the use of activated  carbon
to remove phenolics and other organics from ammoniacal liquors.  The
Calgon Corporation of Pittsburgh, Pennsylvania, has been testing and pro-
posing a system including preclarification, absorption on a moving-bed  of
activated carbon, and thermal regeneration of the carbon.  Several com-
panies are considering this system but none is operational.


By-Product Production of Ammoniacal Compounds

The free ammonia in coke gas and the free and fixed ammonium compounds  in
ammoniacal liquor are frequently recovered, usually by the semidirect pro-
cess as ammonium sulfate by bubbling the gas through a dilute sulfuric  acid
solution in the saturator.  The crystals of ammonium sulfate are separated
from the acid solution by means of a large basket centrifuge and are some-
times further dried in rotary dryers.(2)  This process is widely used in
the United States; however, the value of the sulfate has decreased in
recent years to the point where it is no longer economical.

Theoretically, nitric acid would be an excellent absorbent for the recovery
of ammonia from by-product gases, and the resulting ammonium nitrate would
be a valuable material for both the fertilizer and explosive industries.
Here again, however, the recovery cost exceeds market value of the by-product.

Ammonium thiocyanate has been produced from coke-oven gas by scrubbing  the
hydrogen cyanide in the gas with ammonium polysulfide solution.
                    NH3 + IICN + S  =  NH4SCN


In this process only the ammonia equivalent to the hydrogen cyanide content
is removed.  This amounts to about 20 percent of the total ammonia in the
gas.

It would be ideal if economical methods were found whereby ammonia could be
removed from coke-oven gas and subsequently recovered from the absorption
system to yield a concentrated stream of gaseous ammonia which could then be
condensed to anhydrous ammonia or processed further to any desirable ammonia
chemical or derivative.  At present, ammonia is being removed from by-product
gases by three methods:  (1) by absorption in sulfuric acid to produce
ammonium sulfate; (2) by absorption in phosphoric acid to produce mono- or
diammonium phosphate; and (3) in liquor plants by absorption in water to
yield a dilute ammonia solution from which the ammonia is steam-stripped
and reabsorbed to yield a concentrated 30% ammonium hydroxide solution sold
as B liquor.(12)

The most promising of these chemical processes is the ammonium phosphate
system.   This method involves the absorption of ammonia in an aqueous
solution of monoammonium phosphate which produces a solution of diammonium
phosphate.  The solution is subsequently regenerated by heating, which
strips the ammonia, and restores the monoammonium phosphate solution.
                                     17

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                  H                        NH4
            NH. - PO. + NH  	^- NH  - PO
              4   i  4     3            4  / .  4
                  H
Two processes have been proposed which involve absorption of ammonia to form
ammonium sulfate and subsequent decomposition of the ammonium sulfate to
yield a concentrated ammonia gas stream.  One of the processes involves the
decomposition of ammonium sulfate in the presence of zinc oxide in a moving
bed system.  In the upper part of the reactor ammonium sulfate is decomposed
at 500°C to form zinc sulfate and ammonia according to the following overall
reaction                                                           ,

            (NH4) 2S04 + ZnO - 5 — ZnS04 + 2NH3 + 1^0

In the lower section of the moving bed reactor, the zinc sulfate is decomposed
at 850-1000°C according to the following reaction

            ZnS04 - »— ZnO 4- SO
                                                                            *.

The 803 is converted to sulfuric acid which is used to absorb more ammonia
and the ZnO is recycled with fresh ammonium sulfate.

The second process developed by Inland Steel involves the absorption of
ammonia in ammonium bisulfate solution according to the following reaction
The dried ammonium sulfate crystals are fed to a decomposition chamber heated
to 650°F in which the fused ammonium sulfate is decomposed to gaseous ammonia
and molten ammonium bisulfate according to the following reaction
                 2S04 - ^~- NH3(g) + N

The resulting ammonium bisulfate is recycled.  The ammonia gas can be converted
to anhydrous ammonia gas or absorbed in water to produce an aqueous ammonia.
This process, while interesting, raises certain questions,  llolten ammonium
bisulfate was found to be extremely corrosive to a wide varietv of metals.
                                 18

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Incineration of Ammonia

The Koppers Company has proposed a system for destroying ammonia  in
which the ammonia is absorbed from the coke-oven gas by water-scrubbing.
The weak liquor is stripped with steam to obtain a  concentrated stream
of gaseous ammonia which is burned destructively.(12'  Also  described  in
a U.S. Patent  (13) is a process of burning the stripping ammonia  in  a
regenerator (part of the coke oven) at about 1200°C.  Private  correspon-
dence (14) containing a report by R. E. Muder entitled, "Oxides of
Nitrogen from  Burning of Ammonia" presents his analysis of the proposal
to dispose of  coke plant ammonia by combustion.  He concludes  that
burning of ammonia will not contribute any greater  concentration  of  NO
to the atmosphere than will normal gas combustion.

A brief study  of the thermodynamics of the formation of nitric oxide
during the combustion of ammonia has been made. (I-*)  Thermodynamic data
were obtained  from U.S. Bureau of Mines Bulletin 605 (1963).   The stable
compounds formed during the combustion of ammonia are nitrogen and water.
The only oxide of nitrogen that may be formed in small amounts is NO.
Since nitrogen and oxygen are present during any combustion  involving
air, there is  no thermodynamic reason why more nitric oxide  should form
when burning ammonia than when burning any other compound in air  at  the
same temperature.  If nitric oxide is formed in objectionable  amounts,
it could only  be due to kinetic reasons.  NO might be formed as an
intermediate during the combustion of ammonia and might not  be given a
chance to reach equilibrium, which is unlikely.  The equilibrium  amount
of NO formed increases with increasing temperature.  Hence a cooler
flame will minimize the formation of NO.  A  U.S. Patent granted  to
Rosenblatt and Cohn (!*>) deals with the combustion  of ammonia
                 +  30_  -  2N, + 6H_0
                J     i       2.     2.


The reaction is accelerated at temperatures greater than 500°C using a
precious metal  catalyst.
Ca ta1 ytic Decomp os i tion of Ammonia

There is good reason to believe  that techniques could be developed to
destroy the ammonia by catalytic decomposition either in the coke oven
or in the by-product stream.

The literature on the behavior of ammonia, its synthesis and decomposi-
tion is extensive.  Recent reports by Samples, McMichael, Vigani and
Arthur D. Little, Inc., give numerous references and an extensive review
of the subject. (12., 17, 13, 19)
                                   19

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Ammonia is not a heat stable compound and at high temperatures will
dissociate into its elements, hydrogen and nitrogen, according to the
equation
The rate of decomposition can be increased with certain catalysts.  A
number of catalysts exist.  The most common catalysts are iron oxides.

Considerable insight into the mechanism can be obtained by comparison
between heterogeneous and homogeneous reactions with regard to the
respective energies of activation.  The activation energy for ammonia
decomposition on a tungsten surface is about 41 kcal at 1043°C and more
than 80 kcal without a catalyst at a temperature of 1200°C.(10)

The primary mechanism of ammonia decomposition on iron oxide can be
shown as a two-step process:  (1) chemisorption of ammonia on the iron
catalyst to form iron nitrides and liberation of hydrogen, and (2) the
subsequent desorption of nitrogen from the catalytic surface.  From
studies (20, 21) ±t ±s proposed that the rate-determining step for the
decomposition reaction is the desorption of nitrogen.


                                                  H   H
                		         	_l    I
            2NH  v  ^=""2NH^==5=r 2NH + 2H ^  ^  N - N + 4H
                        *          *     *        *   *    *


                 «t "—. N • N + 6H  •u ~* ' N  + 3H,
                       *   *    *         /     /

Represents a single absorption sight.


White and Melville (22) did some laboratory tests at the University of
Michigan on the thermal decomposition of ammonia in the presence of other
gases.  This early work was done without the intentional addition of any
catalytic agent and consequently, serves as a basis from which to start
other studies.  At 685°C with the following flow rates in cm3/min,
H20 = 4.0, CO = 22.6, NH^ = 90.4 the ammonia decomposition was 27 percent.
From the geometry of the system, the estimated retention time in the
heater at 100 cm3/min is about 11 seconds.  Other of their tests show
that at one atmosphere of pressure, pure ammonia, ammonia with hydrogen,
and ammonia with nitrogen decompose at the same rates.  Some test runs
using a porcelain tube instead of glass resulted in a 50-fold increase
in percentage decomposition.
                                  20

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Charles L. Thomas in his new book "Catalytic Processes  and  Proven  Cata-
lyst" (23) discusses the ammonia decomposition reactions  as follows  -
1 This reaction may not ordinarily be thought of as a dehydrogenation
but it has all the characteristics.  It is used to generate small
quantities of reducing gas, e.g., for metallurgical use.  Catalysts  of
the type used for steam reforming of natural gas, i.e., Ni  on refractory
supports or iron oxide on similar supports, are used."

It would be ideal if means could be found whereby 95% or  more of the
ammonia could be destroyed even before it left the oven.  A British
Patent (<-4) claims the destruction of ammonia during the  coking operation
by the addition of iron oxide in water suspension to the  upper stratum  of
coal in the coke oven.  Up to 95% destruction of the ammonia is shown in
the data presented in the patent, which provides the strongest support
for this method of destruction which has been encountered.
     (25)
Hill      has reported some related studies in regard to  ammonia decom-
position and coke ovens.  It must be remembered that these  investigations
were carried out with the aim of increasing ammonia yield.  He reports
that Foxwell in 1922 found that iron (particularly in its metallic form
in coke oven walls and in coke) was very detrimental as was  lime.  This
effect of the surface material has previously been noted by White and
Melville (in 1905) , who found that fifty times as much decomposition
occurred on rough porcelain as on smooth glass; and by Woltereck (in 1908)
who observed that association started at 320°C in contact with metallic
iron cloth, and at 420°C on oxide of iron.  Heckel (in 1913) had observed
the deleterious action of iron in practical oven tests.  When coal to
which blast furnace dust had been added was coked, the yield of ammonia
decreased tremendously.  Many other investigations were cited (19)
but the conclusions are the same.
                  '<
Wilson and Wells      state that the temperature of formation of ammonia
is not the same for all coals.  For some, ammonia formation begins at
temperatures as low as 300°C, but with others temperatures  in the range
of 400 to 500°C are necessary.  They add that in high-temperature coking,
"the major portion of the ammonia is probably formed at temperatures
above 600°C."  Under favorable catalytic conditions this  temperature
should be high enough to decompose ammonia.  This argument  could be used
to explain the ineffectiveness of attempts to decompose ammonia with flue
dust.  The information on the effectiveness in destroying ammonia by the
addition of iron fines to the coal charge is contradictory.(12)   Near
complete destruction (95%) was obtained when the top of the coal charge
in the oven was covered with a layer of iron oxide.  However, the addition
of flue dust to the coal mixture for ferrocoke resulted in only partial
(20-40%)  destruction of ammonia.

If complete destruction of ammonia can be achieved without  affecting the
quality of the coke, there will be no need for any ammonia  removal equip-
ment.  This incentive justifies further experimental studv  to see whether
essentially complete destruction in the oven is possible
                                  21

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Coke-oven gas after tar removal could be passed through a catalyst bed
that would selectively decompose ammonia.  The extent and rate of cata-
lytic cracking on iron oxide catalysts increase x*ith higher temperatures
and become significant above 500°C and at temperatures around 700°C the
dissociation is complete.  At these temperatures, some of the higher
organics in the coke-oven gas would crack, but the major components from
the standpoint of heating value, methane and hydrogen would be stable.
Also, the remaining important by-product, benzene should be quite stable
at these temperatures, especially in the hydrogen-rich coke-oven gas
atmosphere.  The less important by-products toluene, xylene and naphthalene,
would be progressively less stable at these high temperatures.

For the catalytic cracking of ammonia in the gas stream, four possibilities
have been considered:  1) a fluidized bed with iron as bed material,
2) a moving pebble bed reactor using pebbles of iron or iron oxide pellets,
3) a pebble bed reactor consisting of two stationary beds of pebbles that
are placed on stream and then regenerated periodically and 4) a thicker
brick furnace consisting of two units with one on stream while the other
is being regenerated by burning off deposits on the iron oxide bricks.

The fluid-bed system has the advantage of good gas-solids contact, accu-
rate temperature control, and simplicity in handling of the catalyst.
However, it suffers from higher pressure drop.  The moving bed system is
much too cumbersome and expensive.  The fixed pebble-bed unit has the
advantage of lower pressure drop and simplicity, particularly if the iron
catalyst has long life.  The most promising system appears to be the one
involving parallel-fixed pebble units, using relatively cheap iron ore as
the catalyst.  The catalyst would either be regenerated in place inter-
mittently by controlled oxidation with steam and air, or simply discharged.
To accurately determine cost factors experimental work is necessary to
study operating temperatures, gas velocity in bed, frequency of catalyst
fouling, effect on light oil recovery and effect on the volume and heating
value of the final coke-oven gas.
Ion Exchange for Ammonia.

Ammonia exists in solution predominantly as the ammonium (NH,)+ ion
unless the pH is higher than about 9.5.  The ammonium ion is very similar
to the potassium ion in size and is precipitated by the same reagents
that precipitate potassium.  Absorption of ammonium ion on ion exchange
resins is ordinarily very similar to the absorption,of potassium and
sodium ions.  Therefore, conventional water softening ion exchange resins
whl.ch are selective for calcium and magnesium do a relatively poor job of
removing ammonium from dilute solutions.  Total deionization by mixed bed
ion exchange resins will remove ammonium ions along with other cations
but this process is too costly for wastewater treatment.(27)
                                 22

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Certain zeolites show unusual selectivity for  the ammonium  ion.   A number
of these have been investigated by the Atomic  Energy  Commission because
they also show selectivity for cesium and potassium ions.   A  demonstra-
tion project at the Battelle Memorial Institute, Pacific Northwest
(Hanford Laboratories) showed that certain zeolites including the
naturally occurring mineral clinoptilolite had a high selectivity for
ammonium in natural and wastewaters.

The process employs the natural zeolite which  is selective  for ammonium
ions in the presence of sodium, magnesium and  calcium ions.   Regeneration
of the exhausted clinoptilolite is accomplished with  solutions or
slurries containing lime.  Lime provides hydroxyl ions which  react with
ammonium ions to yield an alkaline aqueous solution.  This  ammonia solu-
tion is processed through an air stripping tower to remove  the ammonia.
The problems of ammonia dispersion to the atmosphere  are similar  to
those encountered in direct air stripping of ammonia.  The  spent  regenerant
is then fortified xtfith more lime and recycled  to the  zeolite  bed  to remove
more ammonia.

A cubic foot of granular clinoptilolite, regenerated with lime, was found
capable of removing ammonia from more than 2000 gallons of  secondary
effluent.  Ammonia removals exceeding 99 percent x^ere obtained for two
clinoptilolite columns in series during laboratory studies.(28)

In a private communication (29) with the Davison Chemical Division,
Baltimore, Maryland, it was stated that they manufactured several  forms
of molecular sieves which are selective for ammonium ions when used as
ion exchangers.  They further state that there is evidence  that thermal
regeneration of these molecular sieves will produce nitrogen  and water
in a catalytic decomposition rather than simply releasing ammonia.  This
possibility should be investigated.  Thermal regeneration occurs  at about
550°C.
Air Stripping of Ammonia

Ammonia stripping is a modification of the aeration process used for the
removal of gases from water.  Ammonium ions in wastewater exist in equi-
librium with ammonia and hydrogen ions as shown by:
            NH  + OH  .. ^      -.NH.on  
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Early studies of feasibility of stripping of ammonia from wastewater
(Kuhn, 1956) showed a major difficulty:  the volume of air per unit
volume of water is very high, about 400 cubic feet per gallon of water
in a countercurrent-flow packed tower.(31)  Ammonia solubility is higher
in cold water than in warm water, consequently, more air is required to
remove it.  For example, at 0°C it would take about 800 cubic feet of air
per gallon of water to remove 90 percent of the ammonia.

There is also a question concerning the magnitude of the air pollution
problem created by the ammonia stripping of ammonia liquors.  In a study
made at Mellon Institute O2) on stripping ammonia from hot excess liquors,
concentrations as high as 6000 mg NHg per cubic meter of air were obtained.
It is unlikely that this concentration of ammonia could be discharged to
the atmosphere.
Reverse Osmosis for Ammonia

Reverse Osmosis (33, 34) involves the forced passage of water through
membranes often cellulose acetate, against the natural osmotic pressure.
The wastewater must be subjected to pressures up to 750 psi to accomplish
separation of water and ions.

Proposed mechanisms for the action of the cellulose acetate membranes
used in reversed osmosis cells include sieving, surface tension, and
hydrogen bonding.  Although plausible, the sieving theory does not
explain the action of the membrane in removing small ions.  For example,
sodium and chloride ions, which are approximately the same size as water
molecules would easily pass through the membrane.

Problems associated with the application of the reverse osmosis process
include concentration polarization, membrane fouling, the passage of
certain ions through the membrane, and disposal of the concentrated
waste fraction.  In a recent study of the use of this process for the
removal of nitrates from irrigation return water, it was found that a
portion of the nitrate ions passes through the membrane, thereby limiting
its usefulness in this application.


Chemical Oxidation or Reduction

The chemistry of aqueous nitrogen compounds is complex and the number of
possible oxidation or reduction reactions is great.  Since nitrogen gas
represents an intermediate redox state for nitrogen and a much desired
end-product for nitrogenous removal, much effort has been devoted to
seeking applicable reactions.  Most of these efforts have been specifically
aimed at the relatively low concentrations of nitrogenous materials
found in sanitary sewage but in principle the results apply to ammoniacal
liquors as well.  Two sets of reactions are possible, oxidation of
ammonia or reduction of nitrate or nitrite to nitrogen gas.  The best
known reaction for the production of gaseous products from the oxidation
                                  24

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of ammonia is the breakpoint reaction with chlorine.  This reaction
requires more than 8 mg/1 of chlorine for each mg/1 of ammonia oxidized.
The chlorination of ammoniacal liquors could utilize electrolytic
production of chlorine because of the inherent high chloride concentration.

Chemical reduction of nitrates in dilute solution has been proposed by
several investigators.  Young, e£ ail, (35) proposed the use of powdered
iron as the reducing agent.  Unfortunately, most of the nitrate  is reduced
to ammonia under the conditions specified.  Gunderloy, e_£ al, (36' made an
extensive study of denitrification by chemical means and  came to the
conclusion that ferrous iron was the reductant of choice.  Results in-
dicate, however, that only about half of the nitrate reduced is  lost; the
remainder becomes ammonia.  An excellent review of the oxidation and
reduction reactions between inorganic nitrogenous constituents has been
prepared by Chao and Kroontje.O/)  In this review numerous potential path-
ways for the production of nitrogen gas from nitrogenous  compounds are
given.  The complexity of the possible reaction schemes makes theoretical
evaluation almost impossible and reliance on experimental information is a
must.  A possible pathway is described which involves ferrous iron
reduction of oxidized forms of nitrogen.  A laboratory evaluation of
this technique was attempted and results are summarized in the Appendix.
                                    25

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                             SECTION V
              BIOLOGICAL OXIDATION AND DENITRIFICATION
BIOLOGICAL OXIDATION OF COKE PLANT WASTES

The use of biological methods for the treatment of various waste waters
from coke plants has been practiced for many years, especially in Europe.
The earliest investigations were concerned with the treatability of
still wastes in conjunction with municipal wastes specifically for the
removal of phenolic compounds.  According to Rudolfs, '3°.) ^g provides
an excellent summary on the biological treatment of coke plant wastes
to 1953, the initial efforts were made in the late 1800's.  These early
experiments concluded that with municipal wastes, with dilution factors
of about 200, satisfactory removals of phenolics and thiocyanates were
possible.  During the ensuing seventy years, numerous efforts, many
highly successful, have been made to treat a variety of ammoniacal
liquors, using both trickling filters and activated sludge, with and
without municipal sewage, and with and without dilution.  Some of these
efforts that have particular historical interest or have direct bearing
on the design of the current experiment are outlined in the following
paragraphs.

The first extensive investigations were reported in 1907 by Frankland
and Silvester (39) who utilized bacterial contact beds and trickling
filters to satisfactorily treat a mixture of 9 percent ammonia still
waste in municipal sewage.  A most interesting experiment was conducted
by Fowler and Holton (40) when they successfully treated ammonia liquor
using a trickling filter of crushed clinker.  Essentially, this plant
consisted of a trickling filter with a recirculation ratio of nine to
one.  This is the first reference to the treatment of ammonia liquor with-
out the use of an external diluent.  Even though these and other
experiments were reported, Key (41) in 1935 concluded that when still
waste does not constitute"more than 0.5 percent of the influent of a
municipal sewage treatment plant, no adverse effects on treatment will
be noted.

The first reported recognition of the fact that ammonia liquors are
deficient in phosphorous is credited by Rudolfs to Nolte in Germany in
1939-   Nolte proposed an activated sludge process supplemented by
available phosphates.

One of the very early efforts in the treatment of ammoniacal liquors in
this country is recorded in a patent assigned in 1922 to the Koppers
Company.(^2)  xhis study, both laboratory and pilot scale, showed that
the phenolic content of properly diluted waste could be greatly reduced.
The first use of activated sludge in the United States for the treatment
of still wastes was by the Milwaukee (Wisconsin) Sewerage Commission
                                   27

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                     (38)
according to Rudolfs     .  These experiments were conducted to determine
if still waste could be treated in a municipal treatment plant.  The
results of this extensive investigation showed that phenolics were removed
as determined by taste test when the mixture treated consisted of 2 per-
cent still waste in municipal sewage.  Additional experimental evidence
indicated that the phenolic wastes could be treated at considerably higher
concentrations and in some cases mixtures containing as high as 15 percent
were treated satisfactorily.

A series of detailed laboratory and field experiments were conducted by
the Chicago Sanitary District and reported by Mohlman (43» 44'.  The treat-
ment criteria defined by these investigations included the limitation on
phenolics of 30 to 40 ppm in the mixture to be treated.  The effect of
temperature on phenolic removal was also noted, removal being enhanced by
increased temperatures.

Two cooperative investigations between the Gary (Indiana) Sewerage Com-
mission and the United States Steel Company have been reported (45, 46)
on the disposal of still wastes in an activated sludge process.  In the
earlier report with a minimum dilution factor of approximately 1 in 40
and an influent phenolics concentration of about 20 ppm, the plant effluent
contained only a few ppb of phenolics.  The latter reference includes the
results of a new series of experiments conducted during 1966-67.  During
this period, a maximum still waste flow of almost 400,000 gallons per day
was treated along with a flow of domestic sewage of about 40 mgd giving
a treatment concentration of only one percent ammonia liquor.  The
approximate aeration time, as computed from data given in the paper, is
nine hours.  The removal of phenolics was essentialljr complete.  A major
obstacle to the discharge of ammonia liquor was the excessive chlorine
demand of the plant effluent.  In the paper, this was attributed to the
more than 16,000 pounds of ammonia being contributed by the ammonia
liquor.  The municipal waste alone contributes approximately 5,000 pounds
of ammonia.  The conclusion that excessive ammonia concentrations were
responsible for this chlorine demand is questioned on the basis that
ammonia exerts a chlorine demand only when subjected to breakpoint chlo-
rination.  The detailed chemistry of breakpoint chlorination is beyond
the scope of the present report but it can be shown that ammonia exerts
no demand until chlorinated beyond a one-to-one molar ratio.  On a weight
basis this corresponds to a ratio of 5 chlorine to 1 ammonia-nitrogen.
Thus, the ammonia in the municipal waste alone would not exert a demand
until after over 60 mg/1 of Cl2 were added and with the combined waste,
over 250 mg/1 would be required.  Since activated sludge plant effluents
generally are disinfected by chlorine dosages of less than 10 mg/1, no
chlorine demand resulting from ammonia would be expected either with or
without ammonia liquor.  The more obvious explanation for the chlorine
demand and the resulting abandonment of the combined treatment program
is unremoved thiocyanate contributed by the ammonia liquor along possibly
with unreacted thiosulfate from the same source.  No actual data on these
constituents is reported.  Approximately 85 percent of the cyanide was
removed in the treatment plant.
                                  28

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The combined treatment of ammoniacal liquors and municipal wastes is
practiced in the Chicago area.  For example, Interlake Steel Corporation
discharges about 60,000 gallons per day of still waste plus some other
coke plant wastewaters and Wisconsin Steel Division of International
Harvester Company discharges about 100,000 gallons per day of undistilled
ammoniacal liquor plus other wastes to the Calumet System of the Metro-
politan Sanitary District.  This apparently successful treatment system
operates at about a one percent liquor concentration.  The East Chicago
activated sludge system accepts about 150,000 gallons per day of lime
distilled and dephenolized liquor from Inland Steel Corporation and
350,000 gallons per day of still waste from Youngstown Sheet and Tube
Company.  The concentration of liquor in this instance is over 5 percent
but much of it has been dephenolized and lime distilled.

Several noteworthy attempts have been made to treat ammonia liquors
without dilution with domestic wastes.  A United States Steel report (47)
outlines a series of experiments utilizing a large scale pilot-plant to
determine the treatability of still wastes containing various concentra-
tions of phenolics.  The results indicate a strong influence of initial
phenolic concentration on the required period of aeration for obtaining
an effluent with less than one mg/1 of phenolics.  To obtain this
effluent concentration required average aeration times of 9.4, 25, and
100 hours for initial phenolic concentrations of 10, 40, and 300 mg/1,
respectively.  Wo mention is made of sludge concentrations involved in
the above tests but the results tend to indicate that they must have
been low.

In 1957, Bethlehem Steel Corporation (^8) began a pilot-plant study which
has evolved into a full-scale treatment facility for ammoniacal liquor.
The general conclusions drawn from the experimental phase of the project  ^
were that phenolic loadings of 30 pounds per day per 100 cubic feet of
aeration capacity could be successfully treated with sludge concentrations
of 5700 mg/1 and a theoretical waste aeration time of 17.5 hours.
Loading rates of this magnitude were not recommended, however, because of
the difficulty in operating the system.  At phenolic loading rates below
about 12 pounds per day per 100 cubic feet and at sludge ratios below
0.7 pounds of phenol per day per pound of sludge the system is reported
to operate smoothly.  Probably the most controversial conclusion from
this work has been with reference to the limiting concentration for
ammonia in the system.  Ammonia is reported to severly inhibit the
biological sludge at concentrations of 4000 mg/1 and the ammonia concen-
tration is considered the :'key design consideration for successful
oxidation of weak ammonia liquor."  Among other important treatment
parameters,found were tar, temperature, nutritional requirements, and
pH.  Recommendations included, limiting ammonia to 2000 mg/1 in the
biological reactor, removal of tar by storage of the liquor at ambient
temperature, maintenance of reactor temperatures of 80-95"F, addition of
phosphorus as phosphoric acid in a ratio of P to phenol of 1 to 70, and
keeping the pH of the effluent between 6 and 8.  The full-scale plant,
                                   29

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designed on these results was put on stream in September of 1962.  This
plant consists of a storage tank, aeration tank, and clarifier,  The
storage tank receives the weak ammonia liquor directly from the coke
plant and provides a detention time of approximately 9 days for equali-
zation and tar removal.   The waste after leaving the storage tank but
prior to its introduction into the activated sludge aeration tank is
diluted with water for control of ammonia concentrations to less than
2000 mg/1, is dosed with phosphoric acid to provide necessary phosphorus,
and is steam heated.  The aeration time, based on the undiluted discharge
of weak ammonia liquor,  is about 56 hours.   Sludge separated in the clarifier
is mostly returned to the aeration tank with excess sludge discharged to
the municipal sewerage system.  The design capacity of this plant is more
than 4000 pounds of phenol per day; the average phenol load only 1300 pounds
per day.  At this loading of less than one-third of design capacity, the
effluent phenol concentration, except during minor upsets, has remained
below 0.1 mg/1.  The efficiency of removal of biochemical oxygen demand
(BOD-5),has been 85-95 percent.  Removals of thiocyanate have ranged from
20 to 99 percent and averaged about 70 percent.

Several methods for improving the plant's capacity for thiocyanate
oxidation and cyanide removal have been pilot-plant tested by Bethlehem
Steel.  These include the following:  (1) a single-stage activated sludge
system in which the effects of many variables were studies, (2) two acti-
vated sludge systems in series, (3) a slag trickling filter in series
with an activated sludge system, and (4) a plastic-media trickling filter
in series with the full-scale plant.  Reportedly, only the treatment on
the slag filter which oxidized up to 2.7 pounds per day of thiocyanate
per 100 cubic feet and removed 50 to 65 percent of the cyanide was
effective.

Just before the Bethlehem Steel Company's plant went on stream, Lone Star
Steel Company (49) ±n Texas began operating a full-scale activated sludge
plant on ammonia still waste liquor.  The plant was designed to reduce
influent concentrations of phenols of 100 to 800 mg/1 to less than one
mg/1 for a waste flow of 50,000 gpd.  The plant provides a pretreatment
storage pond, an aeration time of about 24 hours, a heating unit to
maintain temperatures above 70°F, a caustic feed pump to control p!l in
the range from 7 to 8, a phosphoric acid feeder, and provisions for sludge
recycle.  From the pilot-plant tests conducted to determine design cri-
teria, it was established that treatment efficiency was not enhanced by
aeration chamber oxygen concentrations exceeding 0.5 mg/1.  In actual
practice oxygen levels of 0.7 to 3.0 mg/1 have been iraintained and have
proven to be satisfactory.  A loading factor of 0.2 to 0.25 pounds of
phenolics per day per pound of aerator suspended solids was found to give
optimum results.  The best range for suspended solids in this plant is
2500 to 3500 mg/1.  In actual plant operation, influent phenolic concen-
trations of 250 to 475 mg/1 and effluent concentrations of 0.1 to 0.3
mg/1 have been experienced with partial removal of cyanides.
                                   30

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Dominion Foundries and Steel of Hamilton, Ontario, Canada have been
operating a biological treatment plant processing ammoniacal liquor since
1968.  This plant, as described by Ludberg and Nicks, (50' provides for
tank storage of the x^aste for a period of about 2.5 days, prior to treat-
ment, dilution of the waste to 50 percent strength to control ammonia,
phosphoric acid addition, and aeration time based on undiluted waste of
37 hours, and a sludge recirculation rate equal to the flow of diluted
waste.  The dilution rate is provided to reduce and maintain reactor
ammonia concentrations to less than 1200 mg/1.  From average monthly
data given in the paper, the plant has processed diluted waste concentra-
tions of phenolics ranging from about 260 to 400 mg/1 with effluent
concentrations ranging from about 0.8 to 3.6 mg/1.

The removal of thiocyanate at the Dofasco plant has been erratic.
According to the report, the principal difficulty is that strains of
bacteria that most effectively oxidize thiocyanate function best at
a pH lower than is present in the aeration tank.  The optimum pH for
these bacteria being about 7 with a range of 6.5-7.6.  The actual aeration
tank averages about 8.3.  A longer retention time is also stated to be
beneficial and a second set of aeration tanks operating in series with
the present ones is suggested.

In addition to these actual plant operations, two recent laboratory in-
vestigations are worthy of note.  One of these studies was conducted by
the Koppers Company (51) to determine the treatment necessary to process
crude ammonia liquor, free leg ammonia liquor, and ammonia still waste.
The experiments were conducted in complete-mix activated sludge units
providing an aeration period of 24 hours for a waste diluted to 25 per-
cent  for ammonia control.  Results indicate that the three waste streams
vary  in treatability and that differing design criteria are needed for
each .
 International Hydronics Corporation      has investigated the use of
 several pretreatment steps  for ammoniacal liquors to provide a more
 easily treated waste.  Essentially, the processes proposed remove sub-
 stantial amounts of the ammonia and cyanides prior to biological
 treatment by stripping, chemical precipitation, and coagulation.  Process
 claims include amenability  to biological treatment without dilution.  A
 modified biological system  called Bio-carb which is a mixture of acti-
 vated sludge and activated  carbon is also reported.  This process pro-
 duces an effluent low in carbonaceous materials and especially low in
 odor and color as compared  with other biological processes.

 The scope of this literature review on the biological oxidation of am-
 moniacal liquors has made no attempt to cover the vast numbers of
 references on the subject.  For example, very little of the research
 and experience from either  England or Germany has been included although
 much of this work is reflected in the experiments and operating results
 already described.
                                   31

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However, discussion on the subject of the biological treatment of coke
plant wastes would be remiss without mention of the outstanding paper of
Ashmore, et al (52) in 1957.  This laboratory study on the application
of the activated sludge process to the treatment of carbonization
effluents without sewage was conducted with special emphases on the role
of the sludge and the effect of effluent constituents on treatment.
In these experiments, utilizing completely mixed activated sludge
treatment units, the criterion for successful treatment was reduction of
the 4-hour permanganate value by 90 to 95 percent accompanied by con-
sistent removal of phenolics, thiocyanate, and thiosulfate to a few rag/1.
These studies were conducted on either free or lime distilled liquors.

Among many interesting observations reported were the results of studies
conducted to determine the limiting concentrations of various substances
that could be tolerated by an operating system.  Among the important
limits found was one for chlorides.  The conclusion reached was that am-
monium chloride concentrations as chloride below 2000 mg/1 had no effect
but that larger concentrations were increasingly detrimental.  Data is
given which indicates that at ammonium chloride levels of 10,000 mg/1
as chloride no more than 1000 mg/1 of thiocyanate could be treated
effectively and that this figure fell to 500 mg/1 at a chloride concen-
tration of 20,000 mg/1.  This latter chloride concentration corresponds
to about 8000 mg/1 of ammonia-nitrogen.  However, it was shown conclu-
sively that the detrimental constituent was chloride rather than ammonia
by substitution of sodium chloride for the ammonium chloride in subse-
quent experiments.

In the presence of phenolics, the chloride effect was found to be more
important and for a given concentration of thiocyanate, the chloride
which could be tolerated in the aeration vessel and still permit total
thiocyanate removal, decreased with increasing phenol concentration.
For example, whereas an influent containing 1000 mg/1 of thiocyanate
could be treated in the presence of 10,000 mg/1 of chloride only 2500
mg/1 of chloride could be tolerated when 1100 mg/1 of phenolics were
present in the influent.  This synergistic effect makes extrapolation
from one waste to another both difficult and uncertain.

Other interesting observations for the successful treatment of these
wastes include operation in the endogenous respiration phase to assure
high removals and levels of sludge wastage ranging to ten percent per
day.  Recommended ranges of aerator pH were 6.7 to 7:3.  Cyanide above
a concentration of about 40 mg/1 was found to be inhibitory and when
present along with sulfide was especially bad.  The refractory organics
present after treatment appear to be a most important but poorly under-
stood parameter.  This constituent is known to influence the dilution
necessary for efficient treatment, is associated with the effluent
color, and its detrimental effect is enhanced by heating and high pH.
This latter point along with the fact that calcium thiocyanate is at
about a factor of four more difficult to oxidize than ammonium thiocyanate
may make lime-distillation a poor pretreatment procedure.
                                   32

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BIOLOGICAL NITRIFICATION AND DENITRIFICATION

No previous applications of the processes of nitrification  and  denitri-
fication have intentionally been made  to remove nitrogenous constituents
from amtnoniacal liquors.  The use of these processes has been proposed
to remove ammonia from municipal wastes and both are active mechanisms
in the transformations of nitrogen in  nature.  The basic research  on  the
two mechanisms has essentially all been conducted with  regard to nitrogen
in soil and its affects on agriculture.  Many excellent reviews on these..
processes in these areas are available and include those of Delwiche, (
Fry, (54) and Alexander.(55)  xhe following paragraphs  include  a brief
summary of the pertinent information from these sources.

Nitrification is the biological process of converting ammonia to nitrite
and nitrate.  In nature the two genera of bacteria responsible  for these
changes are Hitrosomonas for ammonia to nitrite and Nitrobacter for
nitrite to nitrate.  These organisms are strictly aerobic chemosynthetic
autotrophs.  This means that these organisms utilize oxygen to  oxidize
ammonia and nitrite to obtain energy to metabolize carbon dioxide  into
cellular materials.  These organisms are truly remarkable when  it  is
considered that they have the ability  to synthesize from carbon dioxide,
bicarbonate, or carbonate the vast array of polysaccharides, structural
constituents, araino acids, vitamins, enzymes, etc., necessary for  life.
The simplicity of their nutritional requirements is of  course accompanied
by a tremendously complex metabolic system.

The capacity of these bacteria to utilize carbon dioxide or other  inorganic
carbonaceous materials depends on their ability to obtain energy from the
oxidation of ammonia and nitrite for the purpose of reducing the inorganic
carbon to organic carbon.  Chemically  these reductions  may  be represented
as follows:

            1)  Ammonia oxidation (Nitrosomonas)

                NH^ + + | 02»—. N02 ~ + H20 + 2H+     F  = ea. -  60  kg. cal./mole


            2)  Nitrite oxidation (Nitrobacter)

                N0_   + i 0  »- NO "                  F  = ca. -  20  kg. cal./mole


            3)  Carbon dioxide reduction

              •• CO  + H9Q-^-CH,0 + 0.                F  = ca. -  120 kg. cal./mole
                  &L    £*      £*     £*
Using these equations,  the approximate  free energies,  and  experimental
results on the amounts  of carbon  assimilated,  the; efficiency  of energy
transformation can be calculated.   The  ratios  of  carbon  assimilated  to
nitrogen oxidized by Nitrosomonas has been found  to vary from approxi-
mately 14 to 70:1 and for Nitrobacter 76  to 135:1.  The  organism efficiency
                                    33

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is then 3 to 14 percent.   A major fallacy in these computations may be
the selection of water as the reducing agent in the conversion of carbon
dioxide with the production of oxygen.  Although this reaction is the     *
primary one in photosynthesis it may not be the major one in this parti-
cular chemosynthetic process.  Thus, the efficiency of the systems are
questionable.  However, the important parameter from a waste treatment
point of view is not the energy requirement but the overall stoichiometry
between the amounts of nitrogen oxidized to the amount of carbon reduced.
If the above ratios of nitrogen to carbon are assumed to hold in waste
treatment, then for every 1000 mg/1 of ammonia-nitrogen oxidized, about
20 and 70 mg/1 of organic carbon would be fixed.  If this carbon is in
the average oxidation state of zero, then this quantity would have a
theoretical, chemical or biological oxygen demand of about 50 to 190 mg/1
as 02-  Concurrently an oxidation resource of almost 3000 mg/1 as Q£ has
been formed as nitrate if subsequent denitrification to nitrogen gas is
assumed.

Some interesting consequences of this fundamental research that effect
the application of this process to waste treatment include bacterial
growth characteristics as characterized by kinetics, pH requirements, and
inhibitors.  Early investigators found these organisms to be very slow
reproducers.  Isolation of pure cultures of the nitrifiers is difficult
because this slow growth favors the more rapidly growing heterotrophs.
A very similar problem occurs in waste treatment.

Nitrifiers are favored by pH levels above 6 and many of the species prefer
a slightly alkaline medium.  Since nitrification is accompanied by the
release of hydrogen ions, unless adequately buffered the process can become
self limiting due to a decrease in pH.  These organisms are known to find
limestone beneficial and tend to coat the mineral.  Both the necessary
buffering and the inorganic carbon requirement are satisfied by the
limestone.

Denitrification occurs when facultative heterotrophic organisms utilize
nitrate and nitrite as an oxygen substitute and produce nitrogen gas.
In the field of agriculture, denitrification leads to a loss of available
nitrogen which is disadvantageous; in waste treatment, the process is
most desirable.  While only a limited number of organisms are capable of
oxidizing ammonia and nitrite, many are capable of reducing nitrite and
nitrate.  Two distinct reduction reactions are possible.  One of these
results in the formation of amino nitrogen which becomes a part of the
cellular synthesis of the bacteria.  The other, true denitrification,
utilizes the two anions, nitrate and nitrite, as metabolic hydrogen
acceptors.  This latter mechanism allows certain organisms to grow
anaerobically in media that would otherwise only support their growth in
the presence of oxygen.

The metabolic pathways for nitrate reduction are not definitely knox^n
and it appears that pathways may be different for differing organisms.
The major postulated reactions are given in Figure 2.  The first step in

-------
reduction of nitrate involves its conversion to nitrite by an enzyme
nitratase.  Some organisms are capable of this reduction step only but
others continue the reduction and many reaction pathways have been
postulated.  Certain organisms are capable of almost quantitative con-
version of nitrite to ammonia, through the amino acid - protein route.
Of the total nitrogen being chemically reduced during intensive
denitrification as practiced in waste treatment, the fraction of nitrogen
reduced through this mechanism will be small.  The major reduction
product of nitrite is hyponitrous acid.  This compound is unstable and
can be further reduced to yield ammonia or nitrogen gas either directly
or through the intermediates nitrous oxide (^0) or hydroxylamine
(HH20U).  The pathways leading to nitrogen gas are, of course, to be
favored for the denitrification of waste waters.
         2NO,
     +4e
                              2NH.
         2W
-------
In addition to indicating the postulated reaction products for denitri-
fication, the figure shows the numbers of electrons, chemical ions, and
molecules involved in the reduction.  The electrons shown are all utilized
in changing the nitrogen to a more reduced state.  These electrons can
only be derived from a chemical oxidation.

In denitrification, this normally is some form of organic material, the
oxidation of which produces carbon dioxide.   These organisms do not
depend on the availability of nitrate or nitrite but utilize these
materials only as a substitute for oxygen when it is unavailable.  Thus,
in the presence of both oxygen and nitrate,  most potential denitrifiers
grow aerobically with little or no effect on the nitrate; without oxygen
they grow anaerobically utilizing nitrate as their electron acceptor.
Most substances utilized for aerobic oxidation are utilized with equal
facility in media containing nitrate.  There are denitrifiers capable of
utilizing sulfur, thiosulfate, and even hydrogen as replacements for
organic carbon as energy sources.

The second major point of note is that two moles of hydrogen ion are
utilized in the reduction of one mole of nitrate to nitrogen gas.  Thus,
denitrification will tend to increase the pll whereas nitrification
lowered it.  In denitrifying concentrated solutions, pH control may be
necessary.

The major environmental influences on denitrification in nature are the
type and amount of organic matter, oxygen concentration, acidity, and
temperature.  The influences on nitrate demand are essentially the same
as those that affect the biochemical oxygen demand except for the oxygen
concentration.  In denitrification the important oxidants are nitrate and
nitrite rather than oxygen as in BOD.  In addition, the presence of oxygen
inhibits denitrification by supplanting a portion or all of the demand of
the organisms for a hydrogen acceptor.

The actual experience with nitrification and denitrification as a mechanism
for nitrogen removal from waste waters is entirely related to its use for
sanitary wastes.  These wastes differ considerably from ammoniacal liquors
from coke plants in that they contain on an average about 20 tng/1 of
ammonia-nitrogen.  Coke plant wastes may contain more than 250 times this
amount.  Therefore, much care must be exercised in attempting to extra-
polate from one waste to another.  However,  much excellent experience has
been gained on this weaker waste and was the background for this phase
of the project.  Among the many papers found to be helpful were those of
Ludzack and Ettinger, (56) Balakrishnan and Eckenfelder, (57, 58) Barth,
Downing, v"°' and Doxming and Hopwood. (61)

Downing was among the first to recognize and define some of the complex
factors involved in maintaining nitrification in a conventional activated
sludge system.  The initial laboratory experiments with coke plant wastes
quickly indicated that nitrification would be most difficult to obtain in
                                  36

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a single-stage activated sludge unit also responsible  for oxidation of
the carbonaceous constituents.  This difficulty results  from several
factors.  The nitrifying sludge population is difficult  to maintain in
sufficient concentration in a single unit because of the necessity of
wasting large amounts of sludge resulting from the  removal of  large
amounts of organic contaminants.  In addition, nitrification is knox^n
to be inhibited by high concentrations of organic materials and by
relatively low levels of heavy metals and cyanogens.   The obvious choice
was to revert to separate carbonaceous and nitrification units in which
sludges and sludge-x^asting could be independently controlled.  With the
addition of the also independent denitrification unit, the plant for
processing coke plant wastes for both carbonaceous  and nitrogenous
removals becomes a three-stage biological treatment operation.  Earth (59)
also has"recommended the use of the three-sludge system.

The first unit of three-sludge system is for the removal of the bulk
of the carbonaceous materials and is essentially the same as a normally
operated activated sludge system.  It consists of an aeration compartment,
sedimentation compartment, capability for sludge recycle, and  facilities
for wasting of sludge.  The second or nitrification stage then receives
for its influent a waste low in carbonaceous matter and  high in ammonia.
This system physically is similar to the first stage which allows inde-
pendent selection of operational variable to maximize nitrification
efficiency.  The third step, denitrification, as a  result of its anaer-
obic nature, is necessarily separate and consists of a mixed reactor
with reductant feed in addition to sedimentation and sludge recycle capa-
bilities.

The reducing agent utilized in the denitrification  stage must be carefully
selected because it can have a large influence on both the ease or diffi-
culty with which the unit operates and on the cost  of  operation.  Finsen
and Sampson (^2) present an excellent review of several  possible reducing
agents  and describe some of their experimental results.  Among those
discussed are various sugars, alcohols, molasses, and  the residual
reductants in treated sewage.  The latter were not  found to be in a form
suitable to act as a hydrogen donor (reducing agent) in  the process.
Sucrose was tried at a ratio of 12 to 18 mg/1 per mg/1 of nitrate-nitrogen.
The use of sucrose was abandoned because the effluent was very turbid and
had a reminiscent of an alcoholic fermentation.  Ethyl alcohol was also
tried.  The alcohol was dosed at 523 parts per million with good results.
However, if it is assumed that the alcohol is oxidized to completion,
this concentration theoretically should have been capable of reducing
more than 380 parts per million of nitrate nitrogen.   When decreases in
alcohol dosage rates were attempted, the unit's behavior became erratic.
Return of the unit to sucrose feed with careful adaptation proved that the
unit could utilize sugar efficiently.  However, the expense of sucrose or
ethyl alcohol was considered prohibitive.  A survey of alternative sources
of hydrogen donors indicated that corn sugar molasses  might be satisfactory,

A major difficulty with molasses was found in the storage and  dosing of
the material.  Diluted molasses suitable for pumping quickly became con-
taminated with bacteria and fungi but addition of 10 percent sodium
                                   37

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chloride to the diluted stock provided a solution to this problem.  Among
the conclusions of Finsen and Sampson concerning the use of molasses were
that an excess of molasses amounting to about 20 mg/1 of chemical oxygen
demand was necessary to get essentially complete denitrification.  The
ratio of molasses utilized as measured by COD as compared to nitrate
reduced was about 50 mg/1 of COD to about 15 mg/1 of nitrate-nitrogen.
                                  38

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                            SECTION VI
                    DESCRIPTION OF PILOT PLANT
The pilot plant was designed to treat excess ammoniacal liquor  at rates
up to 1 gpm.  It was built in modular fashion as shown in Figure 3.
Three nearly identical modules were arranged in series so that  each
successive module would receive treated waste water  from the preceding
system.  The first module was for oxidation of carbon compounds.  The
second and third modules were for oxidation of ammonia to nitrate and
reduction of nitrate to nitrogen gas, respectively.  Each of the modules
were designed as individual and independent treatment systems.  Other
than the dependence of one module on another for a source of waste, the
operating variables of each unit were independent of the others.  Because
of the toxicity of high concentrations of phenols, cyanides and other
compounds in coke plant waste, each of the treatment systems was designed
as a completely mixed activated sludge system.  This design concept was
utilized because it is much less sensitive to high influent concentrations
and large variations in influent composition than other available systems.

Excess liquor from the coke plant tar decanters, flows by gravity to one
of two storage tanks prior to treatment.  These tanks are provided to
reduce the liquor temperature from 150° F to 100° F  or less, the optimum
range for biological activity.  In addition to temperature reduction,
the storage tanks remove tar which escaped the decanters.  It has been
previously reported that the residual tar content of excess ammoniacal
liquor inhibits biological activity. ^^  Each of the storage tanks
has a capacity of 1500 gallons or 24 hours at design capacity.  The tanks
are operated on a fill and draw basis.  Alternately, one tank is cooled
while the other is supplying waste for treatment.

The cool, tar-free liquor is pumped from the storage tank to the first
treatment module for aerobic oxidation of carbon compounds.  The first
module consists of a completely mixed aeration tank  and final clarifier.
Equipment details are listed in Table 3.

The aeration tank is a cylindrical steel tank with a detention  time of
24 hours at 1 gpm.  It is equipped with a 3 horsepower submerged turbine
mixer-aerator.  Compressed air at up to 300 scfm is  spurged under the
turbine to provide oxygen for biological growth.  Temperature control
is provided by live steam injection.  The original control system was
manual but after two occurrences of high temperature sterilization due
to excessive steam flox^ rates, the system was automated.

The effluent from the aeration tank flows by gravity to the center well
of the final clarifier for removal of biological solids.  The clarifier
is a cylindrical steel tank with a cone bottom.  It  has an overflow of
200 gal./day/ft2, and an effective detention time of 150 minutes at 1
gpm.  The clarifier is equipped with a scum baffle,  a vee notch
                                   39

-------
peripheral weir, and spiral sludge rakes.  The settled solids are returned
to the aeration tank with a variable capacity pump.  Recycle rates are
manually controlled between 0 and 1 gpm.  The original system was designed
so that excess sludge could be wasted by periodically diverting the
recycle sludge to the sewer.  This approach proved unsatisfactory and was
later replaced with a system of periodically draining a known percentage
of mixed liquor from the aeration tank to the sewer.

The effluent from the first module flows by gravity to a 55-gallon surge
tank.  This partially treated waste is pumped from the surge tank to the
second treatment module for aerobic oxidation of ammonia to nitrate
(nitrification).  The nitrification system consists of a completely mixed
aeration tank, a final clarifier, and a pH control system.  Equipment
details are listed in Table 3.

The aerator-clarifier system in module two is identical to that described
for the first module with exception that a larger mixer-aerator (15
horsepower) was supplied to adequately handle the greater oxygen demand
anticipated in this system.

A pH control system consisting of a 55-gallon caustic storage tank and a
positive displacement metering pump was provided to maintain the pH between
7.0 and 8.5 in the nitrification system.  Caustic is metered into the
aeration tank at a manually controlled rate to neutralize the nitric acid
produced by the oxidation of ammonia.  Dry sodium carbonate is added in
batch quantities to the aeration tank to supply the nitrifying organisms
with inorganic carbon.

The effluent from the nitrification system flows to a 55-gallon surge
tank.  The nitrified waste is pumped from the surge tank to the third
treatment module for anaerobic reduction of nitrate to nitrogen gas
(denitrification).  The denitrification system consists of a completely
mixed anaerobic growth tank, a final clarifier, and an organic carbon
addition system.  Equipment details are listed in Table 3.

The growth tank is a steam heated, cylindrical steel tank with a detention
time of 8 hours at 1 gpm.  It is equipped with a 1/2 horsepower mixer to
maintain a completely mixed condition.

The final clarifier and sludge handling system is identical to the first
and second modules.

A system for the addition of organic carbon (molasses, methanol, or
sugar solutions) to the growth tank was provided.  The system consists of
a 55-gallon mix tank with a 1/4 horsepower mixer, a 55-gallon pump tank
and a positive displacement metering pump.  The organic carbon compound
is diluted and mixed with water in the mix tank.  This solution is trans-
ferred to the pump tank by gravity and metered at a manually controlled
rate to the growth tank.
                                  40

-------
                                                                                                                                        lOTOMETEK.
                                                                                                                                                               •ORJaANlC CARBON
                                                                                                                                                                 5TOKA&E
       EXCESS
AMMON1ACAL LiaUOR
  STORAGE TANKS
                                                                                              FIGURE  3
                                                                                              PILOT  PLANT

                                                                                            FLOW'UTAGRAM

-------
                  TABLE 3:  PILOT PLANT EQUIPMENT
       Equipment

Storage Tanks

Module I

  Waste Feed
  Dilution Water
  Aeration Tank
  Mixer-Aerator
  Clarifier
  Sludge Recycle

Module II

  Waste Feed
  Dilution Water
  Aeration Tank
  Mixer-Aerator
  Clarifier
  Sludge Recycle
    Feed Rate
                            Size
                                                                       Volume
0
0
    1 gpm
    1 gpm
0-1 gpm
0
0
0
                   6 ft. dia. x 8  ft.  SWD   2000 gal.
               1/4 hp

               5 ft. dia. x 12 ft. SWD   1500  gal.
               3 hp                      v  -
               3 ft. dia. x 3 ft. SWD    150  gal.
               1/4 hp
                   1/4 hp
  Caustic Addition Pump  5 -
1 gpm
1 gpm          -                         .   -
               5 ft. dia. x 12 ft. SWD   1500  gal.
               15 hp
               3 ft. dia. x 3 ft. SWD    150  gal.
1 gpm          1/4 hp
1750 ml./min.  1/6 hp
Module III

  Waste Feed
  Dilution Water
  Growth Tank
  Mixer
  Clarifier
  Sludge Recycle
  Organic Carbon
    Addition Pump
0
0
0
5
1 gpm
1 gpm
                   1/4 hp
                   4 ft. dia. x 6 ft. SWD     500  gal.
                   1/3 hp
                   3 ft. dia. x 3 ft. SWD     150  gal.
    1 gpm          1/4 hp
    1750 ml./min.  1/6 hp
                                   42

-------
Each of the three modules is provided with independent control of waste
volumes and concentrations.  Volume control is provided by 0 to 1 gpm
variable capacity pumps supplying waste to each system.  Dilution water
for adjustment of waste concentration is also supplied to each system.
Dilution water rates of 0 to 1 gpm can be metered into any of the mix
tanks by a manually adjusted flow control system.  The control system
consists of a rotometer and a flow control needle valve.  The use of
these two control systems allows variations to influent flow from zero
to maximum design capacity and simultaneous variations in influent
concentration from zero to full waste strength.

Coke plant waste water is deficient in phosphorus and will not support
biological activity without phosphorus addition.^48> 50' 63> 64^  A
system was installed to continuously feed phosphoric acid to the first
module aeration tank.  The system consisted of a 5-gallon drip pot with
a discharge needle value for the continuous feed of 75% phosphoric acid.
From pilot plant start up, this system was plagued x
-------
                            SECTION VII
                       SAMPLING AND ANALYSIS
The sampling and analysis program conducted during  the pilot plant study
x*as designed to provide:  (1) data required for routine plant operation
and control; and (2) detailed data on vzaste loading, material balance
and process efficiency.  This information was obtained from analysis of
samples taken from twelve sample points as shown in Figure 4.  Samples
from each of these points were collected regularly by the plant operator.
Those analyses and measurements required for routine operation x^ere per-
formed by the operator  in the pilot plant laboratory.  Those analyses
which established plant performance and efficiency but were not required
for routine operation were analyzed in a remote analytical laboratory.
The sampling and analysis schedule used throughout  the study is shown in
Table 4.

Analyses and measurements performed by the operator for routine control
of the pilot plant included  flow rates, temperature, dissolved oxygen,
settleable solids, alkalinity, pH, and dissolved solids.  For convenience
arid simplicity the biological solids level was determined indirectly by
the measurement of settleable solids.  Periodic analysis of suspended
solids were used to  correlate settleable solids data with the more con-
ventional mixed liquor  suspended solids.

In addition to the measurements and analyses performed as a part of normal
plant operation, a supplemental analytical program was conducted at a
remote laboratory.   This program was designed to determine waste loadings,
material balances and treatment efficiencies.  Samples collected at the
pilot plant were preserved by refrigeration during  storage and shipment.
Generally, the analytical work was in progress within four hours of sample
collection.  All analyses were performed in accordance with the recom-
mendations of the 12th  edition of Standard Methods  for theExamination
o f Jffater and Was te Water.

The first treatment  module was designed  for removal of organic carbon
and cyanide compounds.  Total organic carbon and cyanide were selected,
therefore, as indicators of  waste loading, and treatment efficiency.
Influent and effluent analyses for the indicator materials were performed
three days each week.   Difficulties with obtaining  reproducible total
organic carbon results  during the initial part of  the study resulted in
the conversion from  this analysis to  chemical oxygen demand  (C.O.D.).
In addition to the indicator materials,  regular analysis  (weekly or more
frequently) for phenolics, thiocyanate,  sulfide, ammonia, and organic
nitrogen were performed so that  loadings and  treatment efficiencies for
these materials could be determined.
                                  45

-------
EXCESS  AMMONIACAL LIQUOR
T-N-
      STORAGE
       TANK
                 out
  >0
          j-CXh
                STORAGE
                  TANK
                                       DILUTION  WATER    Q
                                                     J
                                                                       F.C.V.  FLOW CONTROL VALVE
                                                                       F.I.   FLOW INDICATOR
                                                                            SAMPLING POINTS
                                                    ORGANIC CARBON
                                                       MIX TANK
        DILUTION WATER
                              CAUSTIC
                       DILUTION WATER
     ,,£
    F.C.V.X
               H3P04 DRIP POT
      AERATOR
        *'«
dy?
            CLARIF.
             *l
             •^ixh
FCV\/
«i   N/
          [F.C.V.
          ]F.I.
        AIR
         (5)
                           OVERFLOW
                           TO SEWER
                                      IF. i.
                                      F.CV.
                                                                   ORGANIC
                                                                    CARBON
                                                                   STORAGE
                                                                  DILUTION WATER
                                                                 4,,.
                                                                                XFC.V.
                            AERATOR
                              #2
dt®
           CLARIF.
:CV\y
Kh    N/^
                                            F.C.V.
                                          «-H*h
                                       JF.C.V.
                                       ]F.I.
                                      AIR
11
                                                                           n
                                                         OVERFLOW
                                                         TO SEWER
                           AERATOR
                             •3a
ci@
                            CLARIF. |
                             *3
                                            ^c.v.  \
                                            >*1    N
       FC.V.
      •*-H>4i
                                                                           <
                                                                           UJ
                                                                           
-------
                                                TABLE 4
                                     SAMPLING AND ANALYSIS SCHEDULE
Parameters
Flow
Temperature
Seechi Disc or Equivalent
pH
Conductivity
Alkalinity
Dissolved Oxygen
Suspended Solids
Settable Solids
Total Organic Carbon
COD
BOD-5
Phenolics
Cyanides
Thiocyanates
Sulfides
Ammonia
Organic Nitrogen
Nitrite
Nitrate
Phosphate

1

D A W P
X
X

X
X
X



X
X
X
X
X
X
X
X
X


X

2

DAW
X
X
X
X
X
X



X
X

X
X
X
X
X
X

X

Sampling Location
3

4 ^5
Sampling Interval"""
DAW
X
X
X
X
X
X



X






X

X
X

D A W P
X
X
X
X
X
X



X

X




X
X
X
X
X
D
X



















1

6

D
X

.

















!

7

D
X





















8

D
X

-•>



















9

D
X





















A

A P






X
X
X










!


B

A , P






X
X
X













c

A P






X
X
X












1.  D - Daily
    A - Alternate Days (Hon., Wed., Fri.)
    W - Weekly
    P - Periodically

-------
The second treatment module was designed for oxidation of ammonia to
nitrate and nitrite followed by the reduction of these compounds in the
third module to nitrogen gas.  As an indication of waste loading and
treatment efficiency influent and effluent samples from both modules
were analyzed three times each week for ammonia, nitrate, and nitrite.
To provide a more complete nitrogen balance across the system, organic
nitrogen was also determined routinely.
                                  48

-------
                           SECTION VIII
                      OPERATIONS AND RESULTS
The operation for almost one year of the three-stage pilot plant resulted
in the collection of much detailed data.  The experiment by its very
design was unsteady and when combined with variations in waste character-
istics and operating difficulties make data interpretations difficult
and somewhat uncertain.  However, in this section an attempt will be
made to present the chronology of operations, the data from the three
operational treatment stages (carbonaceous removal, nitrification, and
denitrification) and to discuss the results obtained in relationship to
operating conditions.  Because of the many variables and the dependency
of the succeeding operating units on previous treatment operations, this
section will present the data and discussion of each unit in the sequence
in which they were operated.

Most of the discussion in this section will be based on summarized data
to be found within this section.  More complete analytical data sets are
provided in the appendixes to this report.  Summarized or averaged data
is used because it reduces both the variability of the data and because
it reduces to manageable dimensions the problem of presenting and inter-
preting the results.  Two methods of selecting averaging periods were
used for the data.  During the early portion of the test, averaging
periods were chose to represent periods in which a single batch of
waste was used as the plant influent.  This period was characterized by
use of high dilution rates which allowed the use of a uniform influent
(one filling of a storage tank) for periods of several days.  This per-
mitted the averaging of several determinations for most variables.  As
dilution rates decreased, the time required to empty a waste storage
tank decreased to little more than one day.  During these intervals an
arbitrary averaging period of about one week was selected.

In the tables to follow, the averaging period for the successive stages
of operation have been selected so as to represent as closely as possible
a slug of waste passing through the treatment complex.  In other words,
as a first approximation, the averaging periods have been selected to
represent periods corresponding to the delay based on detention times.
Thus, the averaging period for the nitrification and denitrification
unit lag by one and two days, respectively, the period selected for the
carbonaceous unit because of the 24-hour detention times used in both
the first and second treatment units.  The numbers used for designating
the operational periods in the tables of this section are days of
operation counting from 1 February 1970.
                                  49

-------
THE EXCESS AMMONIACAL LIQUOR

Before proceeding with a discussion of each of the sequential treatment
units, a description of the character of waste itself through the
experiment is necessary.  Waste strength and variability are most
important parameters in the operation of biological treatment systems.
The characteristics of the waste for the averaging periods are given in
Table 5 and a summary for the major characteristics of the waste are
given in Table 6.  (Detailed data is included in Appendix A-l.)  These
results show the waste to be highly variable in chemical oxygen demand,
phenolics, thiocyanate, sulfides, and organic nitrogen, but less so in
ammonia.  Actually of more importance to waste treatment than simply
the variability of waste strength is the rate of change in the concen-
trations of the constituents.  From Table 5, it is apparent that changes
from one averaging period to another can exceed a factor of 2 for COD
and approach this factor for phenolics, thiocyanate, and ammonia.  These
variations must be dampened prior to entry into a biological plant if
overloads and underloads are to be avoided.

An important criterion for the operation of biological systems treating
excess ammoniacal liquor is the percentage of liquor being treated.
Influent dilution factor is one of the major controls the operator has
on the system.  Two approaches are available for estimating the actual
dilution rate used at a specific time.  First, the operator attempted
to establish a specified dilution rate by pump adjustments and monitored
the flow rates for both the liquor and dilution water (given in Appendix
B-l).  However, because of variations in flows, a better estimate of
actual dilution rates was possible through the use of a materials balance
computation for conductivity.  Conductivity was chosen because it is a
conservative constituent, that is, the concentration is not affected
significantly by the treatment.  In addition, the large difference between
the conductivities of the waste and the dilution water makes the computa-
tion more reliable.  Since conductivity is a measure of dissolved solids,
the conductivity in and out of the treatment system is hypothesized to
be equal.  This may be written as


            VD + VL = % + VCE
where
            QD = quantity of dilution water,

            QT = quantity of liquor,
             LI
            C  = conductivity of dilution water,

            C  - conductivity of liquor, and
             LI
            CE = conductivity of the effluent,
                                 50

-------
TABLE 5 - EXCESS AMMONIACAL LIQUOR
PERIOD
1-5 2/1-5
6-13 2/6-13
14-21 2/14-21
22-29 2/22-3/1
30-39 3/2-11
40-43 3/12-15
44-48 3/16-20
49-55 3/21-27
56-57 3/23-29
53-60 3/31-4/1
61-67 4/2-8
63-73 4/9-14
74-76 4/15-17
77-81 4/18-22
82-84 4/23-25
85-88 4/26-29
89-91 4/30-5/2
92-95 5/3-6
96-98 5/7-9 •
99-103 5/10-14
104-108 5/15-19
109-112 5/20-23
113-116 5/24-27
117-121 5/28-6/1
122-129 6/2-9
130-136 6/10-16
137-143 6/17-23
144-150 6/24-30
151-157 7/1-7
158-164 7/3-14
165-171 7/15-21
172-173 7/22-28
179-135 7/21-8/4
186-192 3/5-1 1
193-199 8/12-18
200-206 3/19-25
207-213 3/26-9/1
214-220 9/2-3
221-227 1/9-15
228-234 9/16-22
235-241 °/23-29
242-248 9/30-10/6
249-255 10/7-13
256-262 10/14-20
263-269 10/21-27
270-276 10/28-11/3
277-281 11/4-10
234-290 11/11-17
291-297 11/18-24
298-104 11/25-12/1
105-311 12/2-',
112-318 12/9-15
119-125 12/16-22
176-332 12/23-21
313- Til 12/30-1/1
') '.0-346 1/6-12
!•'' 7-152 1/13-18
5.
8.5
8.7
3.9
8.7
8.8
8.7
8.4
8.7
9.1
8.9
8.8
8.6
8.5
8.4
8.5
8.4
8.4
8.5
8.6
8.6
8.6
8.5
8.6
3.6
8.6
8.6
8.6
8.5
3.4
8.4
8.3
8.4
8.4
8.5
3.6
8.5
3.6
8.6
8.6
8.6
8.6
8.6
8.6
3.7
8.7
8.6
8.6
8.7
3.6
8.4
3.5
8.7
S.6
8.6
8.7
8. 7
8.7
ALKALINITY
mg/1
CaC03
1330
1630
2540
1760
1870
1520
1220
•1600
27 00
2630
2170
1810
1730
1680
1560
1360
1340
1420
2100
1440
1660
1750
1730
1820
2000
1590
1440
1630
1300
1330
1230
1400
1450
1430
1500
1690
1650
1830
2290
2230
2290
2610
2410
2190
2120
1630
1840
1890
1330
1540
1490
2370
1970
I '100
2190
2240
2190
CONDUCTIVITY
jumhos
15400
14100
10900
12800
12200
13900
14250
16700
13300
14200
12500
12100
21000
24450
26400
23400
23900
21200
20000
20400
23400
20700
21000
18900
20700
24200
29400
24600
25800
26200
26500
24700
22700
19600
20000
21300
15000
21500
28500
28500
22300
26500
28000
27500
29300
26300
29200
27400
26300
23200
27600
29900
31800
30700
21700
1120')
29300
ORGANIC
CARBON
mg/1 C
700
720
760
760
730
1370
1450
1480
1140
1700
2360
2030
2970
3700
2660
1990
1920
1260
1670
1650
1510
1600
930
1070
1700
1200
510
460
720



1290


880





















a ---
Sic?






3630










3400








2920
3460
3360
3170
2900
2830
2460
2700
2930
3260
3350
7670
9230
9010
9120
10400
9600
9720
3180
5420
3660
5770
5130
5740
3660
6600
5710
6520
6750
5330
5330
m ~*
!»«?






2330










1710










1830









6170


5790

.

2460




4160



4030


PHENOLICS
mg/1
PHENOL
500
410
500
525
530
780
765
645


930
730

1330

850

560

665

850
830

700
900
650
650
580
490
540
-
420
500
550
710
1240
1700
1860
1900
2150
2380
650

950
920
1070
1 080
11 10
1120
1430
1130
I 100
1290
13!')
101"
1200
CYANIDE
mg/1
CN
10
23
32
27
22
17
10
15
37
16
21
28
25
26
21
21
24
28
30
32
35
24
36
30
36
30
23
25
28
27
27
26
26
23
25
21
27
13
14
11
18
22
19
10
18
25
35
20
18
20
13
32
26
23
1 7
22
23
THIOCYANATE
mg/1
SCN
250
210
190

250
250
240
290


175
240

390

550

400

360

230
100

410
360
290
370
350
300
310
-
300
320
290
430
140
530
770
1540
630
1100
660

480
540
640
•540
560
1)0
690
650
640
650
670
610
650
SULFIDES
n.g/1
S
0
7
50

22
4
0
0


23
2

2

0

2

3

3
6

0
0
0
0
0
0
0
-
2
0
4
2
2
1
1
1
2
2
4

0
1
•)
3
1
0
1
4
1
4
1
•)
2
AMMONIA
mg/1
N
1860
1910
1800
1920
1900
1960
1890
1780
2250
2010
1960
1880
3110
3570
4170
3500
3740
3200
3490
3350
3630
3400
3400
1100
3400
3850
3880
3740
3620
3620
3530
3270
3170
2720
2840
3040
2200
1030
4180
4120
1150
4020
1960
3780
4200
3630
4070
3750
3610
1S50
1810
-',190
4290
2490
202')
2040
1790
S§z
3Sk
ss«
ggt
100
115
90

90
100
90
100


70


250

200

120

200

190
225

15
375
180
180
180
150
260

100
110
120
140
140
150
230
200
170
190
260
-
230
200
200
90
140
170
260
180
250
700
2300
2 1 00
80
TOTAL
NITROGEN
mg/1 N
1970
2040
1910

2000
2070
1990
1890
	
—
2040
—
—
3830
	
3710
—
3340
—
3570
__
3600
3640
—
3440
4240
4070
3930
3820
3780
3800
—
3280
284fl
2970
3190
2350'
3190
4420
4330
3530
4220
4210
—
4440
3840
4290
1850
3760
4030
4080
4390
4550
1200
4330
4150
3880
                  51

-------
Since the only contributors of solids and liquids to the system are the
dilution water and the liquor and neglecting any losses in the blowdown,
this equation can easily be reduced to give for the fraction of liquor
being treated,
                   Q
                                                                     (2)
                    D
The solution of this equation requires the knowledge of the conductivities
of the dilution water, liquor, and effluent for each averaging period.
                                                               ^ •   A 1
Values of the conductivities for the liquor are given in Appendix A-l
and for the effluent from the carbonaceous unit in Appendix A-2.  The
conductivity of the dilution water was by comparison low and was relatively
constant throughout the test.  A constant value of 600 micromhos per cm.
has been assumed for the conductivity of the dilution water.
TABLE 6;  SUMMARY OF CHARACTERISTICS - EXCESS AMHONIACAL LIQUOR
Parameter        Mean     Median

pH                          8.6

Alkalinity       1800      1700
mg/1 CaCO.


Conductivity    23000     23000
umhos/cm2

COD              5800      5700
mg/1 02

Phenolics         950       850
mg/1 Phenol

Cyanide            24        23
mg/1 CN

Thiocyanate       470       380
mg/1 SCN

Sulfides          3.7         2
mg/1 S

Ammonia          3200      3400
mg/1 N

Organic N         270       180
mg/1 N
Standard Deviation
        390
       5800
       2500
        460
        260


        8.2


        800


        430
    Range

  8.3-9.1

 1200-2700



11000-32000


 2500-10000



  410-2400


   10-37


  100-1500


    0-50


 1800-4300


   15-2300
                                 52

-------
CARBONACEOUS TREATMENT UNIT

The carbon removal unit began operation  on  8  January  1970 when  an  influent
flow of one (1) gallon per minute  of  a 15 percent  dilution  of excess
ammoniacal liquor was initiated.   This flow rate represented an aeration
time of approximately 24 hours.  Phosphoric acid was  added  according  to
the schedule given in Section VI.   The system was  seeded on 8 January
with unknown quantities of three different  materials, Bethlehem Steel
biological solids, soil from in and around  the  Houston  Coke Plant  by-
products area, and final clarifier sludge from  the Houston  Works trickling
filter sewage plant.  Unfortunately,  the system was pasteurized on
15 January by the accidental increase in aeration  tank  temperature above
150° F.  The system was restarted  on  16  January and seeded  with the same
materials previously used.

The remainder of the month of January was basically used for adapting
organisms to the waste, accumulating  organisms, and learning to operate
the unit.  During this period recycle flow  was  one (1)  gallon per  minute
and no sludge was intentionally wasted.  On 1 February  collection  of
operating and analytical data was  begun.

Table 7 summarizes the operating information  for the  individual averaging
periods for the carbonaceous unit. More detailed  information can  be
found in Appendix B-l.  Table 8 gives the chemical composition  of  the
influent to the unit and Table 9 gives the  effluent quality, percent
removals, and loadings.  These three  tables provide a summary of the
chronology of operation, the data  obtained, and the problems encountered.

The results of the computation for percentage of waste  in the influent
are given in both Tables 7 and 8.   The original project plan called for
increasing waste percentages in a  consistent  manner.  However,  because
of unit upsets which will be discussed later, several reductions in
liquor percentages were found to be necessary in order  to maintain adequate
treatment levels.  A plot of the percent waste  treated  in the carbonaceous
unit for the duration of the test  is  given  in Figure  5.

In addition to the waste concentration being  treated, Table 7 provides
data on several other operational  parameters.  Among  items  of major
interest are reactor temperature,  pH, dissolved oxygen, and suspended
solids.  Also included are measures of  the  clarity of the effluent (Seechi
disk), blowdown rate, chemical additives used and  special operational
condi tions en counte red.
                                  53

-------
TABLE  7;    OPERATING CONDITIONS. CARBON REMOVAL UNIT



PERIOD
i
1-5
6-13
14-21
22-29
30-39
40-43
44-48
49-55
56-57
58-60
61-67
68-73
74-76
77-81
62-84
85-88
89-91
92-95
96-98
99-103
104-108
109-112
113-116
117-121
122-129
1 30- 1 16
137-143
144-150
151-157
158-164
165-171
172-178
179-165
166-192
193-199
200-206
207-211
214-220
221-227
228-234
2I5-2M
2V2-248
2-.9-25S
256-262
263-269
270-276
277-283
284-290
291-297
298-104
105-311
312-318
319-325
326-132
111-319
340-346
147-152

B
fi'l
INFU'E
PERCENT

13
15
17
15
15
16
16
15
22
29
23
27
25
14
16
42
38
47
61
64
57
70
76
73
82
89
56
65
60
54
49
72
78
74
74
74
86
71
68
79
81
75
40
17
2)
41
47
58
10
22
15
45
45
58
49
46
57
b.

a"
TEMPERATI

80
76
79
80
82
77
80
78
80
81
82
80
8!
82
85
85
79
76
79
86
83
85
86
86
84
90
89
89
88
89
88
87
90
91
88
89
85
89
90
90
84
78
76
75
82
72
72
70
7)
77
89
90
86
88
89
91
86



x
a.

8.3
8.1
8.0
8.2
7.8
6.6
6.4
7.5
7.5
7.0
7.8
8.5
8.3
8.1
8.1
8.1
7.8
7.6
8.3
8.3
8.2
8.2
8.2
8.3
8.3
8.3
8.2
8.1
8.0
8.0
6.0
8.1
7.9
8.1
8.2
8.2
8.0
7.9
7.9
7.8
7.9
8.0
8.0
8.1
8.0
8.1
8.2
8.2
8.2
8.1
8.1
8.2
8.2
8.1
8.3
8.2
8.2

(v
a

DISSOLVED
OXYGEN, me




















2.7
3.7
4.1
2.8
2.3
2.0
1.
2.
2.
2.
I.
1.
1.
1.
1.0
1.9
1.2
1.0
1.1

0.8
2.7
2.3
2.8
3.0
2.3
2.3
2.6
2.5
1.0
2.4
2.0
2.0
2.0
2.2

o
g
s»
REACTOR SI':
SOLIDS , 1


































1420
1220
700


250
100
140
850





tolioff
Cone
«1/1
K
a o
sg
X >J

0
5
10
19
36
73
49
70

62
41
34
34
36
190
180
200
170
160
210
280
210
180
180
130
80
45
50
39
53
57
84
160
120
140
70
140
170
160
140
40
8
8
2
4
15
12
3
1
4
65
190
180
220
280
260
260
RETURN
SLUDGE

3
18
21
40
63
140
100
170

140
61
49
94
340
740
400
400
290
600
610
700
540
380
360
240
125
90
100
78
108
79
180
210
240
220
210
210
310
280
190
30
8
8
2
1
16
16
6
5
5
90
330
360
400
450
430
560

,
X
U*
SECCHI D:
INCHES


8
7
8
11
9
9
6
6
5
5
4
5
3
4
4
3
3
3
4
4
3
4
4
2
2
2
3
3
3
3
1
4
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
3
4
4
3
3
3
3
2
1



BLOUDOWN,
PERCJNT/DA1



2
2
'i
2
2-6
4-6
4
2-6
2
2
2
2
2
2
2
2
2
2
2
2
2
2-6
2-6
2
2
2
2
2
2
2
2
2
0
0.5
1
1
0.5
0.5










Chemical Additives per Period

mi.
OSPHORIC
ACID
£

e
41
E
i
u
41
f
ui



750










750
1500
1300
2900
2800
2200
1500
2200
2200
2200
3000
1500
2200
15OD
1500
2200
2200
2200
2200
1500
JCOO
750
750
1500
2200
1500
750
15QO
750
750
2200
1500
1500
1500
1500
RIBUTYL
HOSPHATE
H 0.










30
50

100

125
125



150
250
225
570
450
100
300
300
300
500
300
500
300
300
300
400
500
600
400
800
100
100
300
500
300
ISO
300
150
150
400
300
200
200
300
pounds
IMESTONE
^





3








































li
ta _i















































is
£







2
in





































ODIUM
ARBONATE
w u





I
2
4

5


























2









Special Conditions


5
K
^_








X
X


X
X
x

x
x

)(



x
x



X
X



x
X

X
X

x

X




X


z
*







x
X
X
X


x
x










X
x

x
x





X


x

y


X


X
z
1
SSOLVED 0X1
S
























X




X

X
X

X












S
TEMPERATU










X





























X
X
X








|

X




X





X


X

X



x
x

x
X
x

x

X

X
X
x
x
X
x

X

x
X


X

X
X

a
3
V)
%.







X




x





































COMMENTS

3 mi per 4 gals, undiluted
waste, phosphoric acid.







(64) Temp.- 123'F.














0.0. not available.
(136) D. 0. - 0.2 mg/1.




(173) D.O. = 0.1 mg/1.

(199) D.O. • 0.5 mg/1.
D. 0. marginal.

(223) D.O. - 0.3 mg/1.

D. 0. marginal
System reseeded.

(278) Temp.- 64°F.
(289) Temp." 61'F.
(297) Tenp.- 62°F.
Heating reactor.





                      54

-------
TABLE 8:   INFLUENT. CARBON REMOVAL UNIT
PERIOD
1970-71
1-5 2/1-5
6-13 2/6-13
14-21 2/14-21
22-29 2/22-3/1
30-39 3/2-11
40-43 3/12-15
44-48 3/16-20
49-55 3/21-27
56-57 3'28-29
58-60 3/30-4/1
61-67 4'2-8
68-73 4/9-14
74-76 4/15-17
77-81 4/18-22
82-84 4/23-25
35-88 4/26-29
89-91 4/30-5/2
92-95 5/3-6
96-98 5/7-9
99-103 5/10-14
104-108 5/15-19
109-112 5/20-23
113-116 5/24-27
117-121 5/28-6/1
122-129 6/2-9
130-136 6/10-16
137-143 6/17-23
144-150 6/24-30
151-157 7/1-7
158-164 7/8-14
165-171 7/15-21
172-178 7/22-28
179-185 7/29-8/4
186-192 8/5-11
193-199 8/12-18
200-206 8/19-25
207-213 8/26-9/1
214-220 9/2-8
221-227 9/9-15
228-234 9/16-22
235-241 9/23-29
242-248 9/30-10/6
249-255 10/7-13
256-262 10/14-20
263-269 10/21-27
270-276 10/28-11/3
277-283 11/4-10
284-290 11/11-17
291-297 11/18-24
298-304 11/25-12/1
305-311 12/2-8
312-318 12/9-15
319-325 12/16-22
326-332 12/23-29
333-339 12/30-1/5
340-346 1/6-12
347-352 1/13-18
PERCENT
WASTE
13
15
17
15
15
16
16
15
22
29
23
27
25
34
36
42
38
47
61
64
57
70
76
73
82
89
56
65
60
54
49
72
78
74
74
74
86
71'
68
79
81
75
40
17
23
43'
47
58
30
22
35
45
45
58
49
46
47
ORGANIC
CARBON,
mg/1 C
90
110
130
115
110
220
230
220
250
500
550
550
740
1260
950
840
730
590
1020
1050
860
1120
710
780
1390
1070
290 (?)
300(?)
430



1000


650





















f-t
8 to






580










1600








1640
2250
2000
1710
1420
2040
1920
2000
2170
2400
2880
5500
6300
7100
7400
7800
3800
1650
1900
2320
4100
3350
1550
1260
3030
3000
2570
3800
3300
2680
2740
I-






370










800










1100









4200


4300



1050




1460



1980


PHENOLICS
mg/1
PHENOL
66
.60
85
80
80
120
120
100


210
200

450

350

260

430

590
480

570
800
360
420
350
260
260
-
330
370
410
530
1100
1200
1260
1500
1750
1800
260
-
220
400
500
630
330
250
520
520
500
750
640
470
560
CYANIDE
ng/1
CN
1.3
3.5
5.5
4.1
3.4
2.7
1.6
2.2
8.1
4.6
4.9
7.7
6.4
8.9'
7.7
8.8
9.1
13.4
18.3
20.4
20.0
16.8
27.4
21.9
29.6
26.7
12.9
16.2
17
15
13
19
20
17
18
16
19
9
9
15
15
16
8
2
4
10
16
12
5
4
6
14
12
13
8
10
12
' THIOCYANATE
mg/1
SON
33
32
32

37
40
38
43


40
65

130

230

190

230

160
75

340
320
160
240
210
160
150

230
240
210
320
120
380
520
1200
510
820
260

110
230
300
310
170
80
240
290
290
380
330
280
310
<:
M _i
|f«
240
290
310
290
280
310
300
270
500
580
450
510
780
1210
1500
1470
1420
1500
2130
2140
2070
2330
2580
2260
2780
3420
2180
2440
2170
1960
1730
2360
2480
2020
2100
2300 .
1900
2200
2800
3260
2700
3000
1600
640
960
1560
1900
2170
1080
850
1340
1830
1930
1440
1000
940
1780
ORGANIC
NITROGEN
mg/1 N
13
17
15

13
17
14
15


16


86

84

56

125

130
170

10
330
100
120
110
80
130

80
80
90
100
120
110
160
160
140
140
100

50
90
100
50
40
40
80
80
110
410
1130
970
40
H M 6
250
310
330

290
330
310
290


470


1300

1550

1560

2270

2520
2750

2790
3750
2280
2560
2280
2040
1860
—
2560
2100
2200
2400
2020
2310
2960
3420
2850
3140
1700
—
1010
1650
2000
2220
1120
890
1420
1960
2040
1850
2130
1910
1820
PHOSPHATE
rag /I
P

















44









61,




50





49



0.8


34



60







                      55

-------
TABLE 9;   LOADINGS AND REMOVALS. CARBON REMOVAL UNIT
PERIOD
1-5 2/1-5
6-13 2/6-13
14-21 2/14-21
22-29 2/22-3/1
30-39 3/2-11
40-43 3/12-15
44-48 3/16-20
49-55 3/21/27
56-57 3/28-29
58-60 3/30-4/1
61-67 4/2/8
68-73 4/9-14
74-76 4/15-17
77-81 4/18-22
82-84 4/23/25
85-88 4/26-29
89-91 4/30-5/2
92-95 5/3-6
96-98 5/7-9
99-103 5/10-14
104-108 5/15-19
109-112 5/20-23
113-116 5/24/27
117-121 5/28-6/1
122-129 6/2-9
130-136 6/10-16
137-143 6/17-23
144-150 6/24-30
151-157 7/1-7
158-164 7/8-14
165-171 7/15-21
172-178 7/22/28
179-185 7/29-8/4
186-192 8/5-11
193-199 8/12-18
200-206 8/19-25
207-213 8/26-9/1
214-220 9/2-8
221-227 9/9-15
228-234 9/16-22
235-241 9/23-29
242-248 9/30-10/6
249-255 10/7-13
256-262 10/14-20
263-269 10/21-27
270-276 10/28-11/3
277-283 11/4-10
284-290 ll/ll-H/17
291-297 11/18-24
298-304 11/25-12/1
305-311 12/2-8
312-318 12/9-15
319-325 12/16-22
326-332 12/23-29
333-339 12/30-1/5
340-346 1/6-12
347-352 1/13-18
ORGANIC CARBON
Effluent 1
mg/1 C I
32
27
30
20
IB
22
16
19
25
35
144
47
44
94
66
82
66
57
150
53
140
62
48
90
130
270
40
24
53


41



72





















Influent 1
Loading I
Parameter j
230
20
14
6
3
3
5
3

8
13
16
22
35
5
5
4
3
6
5
3
5
4
4
10
13
6
6
11


6



9





















»4
a
"I
64
65
77
82
84
90
93
91
90
93
71
91
94
93
93
90
91
90
85
95
84
94
93
88
91
75
86
92
88


.



89





















	 CHEMICAL 	 1
OXYGEN DEMAND
Effluent 1
mg/1 02 |

























1700
950
800
700
690
620
1040
770
700
750
1000
790
840
1740
2400
2080
2740
1550
610
630
770
1100
1130
650
400
490
710
710
700
630
750
730
Influent
Loading 1
Parameter |


























36
45
51
32
25
24
12
17
15
35
21
32
39
51
180
1000
470
820
480
150
340
1100
1500
320
46
16
14
17
12
10
11
Removal 1


























42
65
65
60
56
49
60
65
65
59
72
67
73
66
72
65
59
63
67
67
73
66
58
68
84
76
72
82
81
72
73
FHENOUCS
w
c
«»ri •*
»•- 0
** M a
«H E 01
lu £
U K
O.I
0.2
0.2
0.4
0.1
0.1


0.0

124
0.2

0.1

0.2

1.0

0.1
0.2

0.2
5.0
0.6
0.6
0.3
0.2
0.2
0.2
0.2
*
0.3
0.2
0.2
0.3
0.2
0.2
1.0
1.2
11.
16.
0.2
-
0.2
0.2
0.6
4.3
0.4
0.1
0.1
0.2
0.1
0.3
0.2
0.3
0.2
[ Influent
Loading
1 Parameter
170
11
9
4
2
2
2
I


5
6

12

2

2

2

3
3

4
10
8
6
9
5
5
m
2
3
3
8
8
7
8
11
44
220
32

55
27
42
210
330
62
8
3
3
3
2
2
2
CYANIDE
Effluent 1
«g/l CS 1
0.6
0.9
0.7
0.9
1.1
2.1
3.4
2.0
1.3
3.2
1.6
1.1
1.5
4.1
4.9
3.2
2.7
3.6
5.8
7.6
4.7
10
20
5.2
7.0
7.0
4.9
5.2
8.6
4.0
3.7
5.0
5.6
5.0
6.0
5.4
3.5
4.5
4.7
4.5
6.7
5.6
3.4
1.7
2.1
4.8
4.8
9.6
3.0
2.6
4.1
5.7
6.3
5.5
4.6
5.1
5.3
1 Influent
Loading
Parameter
3
0.6
0.6
0.2
0.1
0.04
0.03
0.03

0.07
0.1
0.2
0.2
0.2
0.04
0.05
0.05
0.08
0.01
0.09
0.07
0.08
0.2
0.1
0.2
0.3
0.3
0.3
0.4
0.3
0.2
0.2
0.1
O.I
0.1
0.2
0.1
0.1
0.1
0.1
0.3
2
1
1
1
0.6
1.
4
5
1
0.1
O.I
O.I
0.1
0.0
0.0
0.1
r*
9
"I
54
74
87
78
68
22

10
84
30
67
86
77
54
36
64
70
73
68
63
76
40
26
76
76
74
62
68
50
73
72
74
72
71
67
66
82
50
48
70
55
65
57
15
48
52
70
18
40
35
32
59
48
58
43
49
56
THIOCYANATE
Effluent
mg/1 SCN
32
39
26
35
22
•17


12

86
64

79

113

22

164
86

198
180

340
240
154
160
170
170
.
190
250
220
270
140
270
390
1220
390
630
150
510
220
190
290
310
140
180
250
280
280
280
280
290
280
b
u «
S2S
1!
82
6
2

1
1
1
1


1
2

4

1

1

1

1


3
4
4
5
5
3
3
.
1
2
2
5
1
2
3
9
13
100
32
-
27
15
25
100
170
20
4
2
2
2
1
1
1
**
a
" 1
0
0
20

40
57





0

40

50

88

30







35
24
0
0
.
17
0
0
15
0
29
44
0
24
23
32
.
9
17
3
0
17
0
0
0
0
26
15
0
10
AMMONIA
1 Effluent I
k"
200
265
240
220
200
210
200
230
280
410
320
340
600
950
1220
1260
1190
1290
1700
1580
1780
1970
2370
1740
2500
2950
1940
1950
1880
1670
1550
2080
2090
1780
1830
1870
1480
1850
2320
2670
1630
2340
1350
510
760
1240
1610
1890
900
790
1090
1600
1760
1120
820
770
1680
1-4
CS
H I
17
9
24
24
28
33
34
16
35
30
30
34
23
21
19
14
16
15
20
26
14
17
8
23
10
14
11
20
13
15
10
12
16
12
13
19
22
16
17
18
40
22
16
20
21
20
15
13
17
7
19
15
9
22
18
18
6
TOTAL
(Effluent
mg/1 N
230
300
270
240
280
320


360

350
380

1000

1300

1350

1660
1890

2580
1800

3150
2040
2060
1930
1760
1700
.
2210
1860
1920
1940
1590
1960
2490
2820
1800
2470
1450
»
950
1310
t710
1950
970
850
1140
1640
1800
1520
1750
1660
1750
N
r*
ed
** 1
a.
18
3
18

4
3




25
•

23

16

19

27


6


14
10
19
15
14
9
.
14
11
13
19
21
15
14
18
37
23
15
-
6
21
15
12
14
5
20
16
12
18
18
13
4
                        56

-------
Ul
        IOO-



         90-



         8O-
       iu
       Ul
       u
       (C
       UJ
         60-
         50-
340
u.
z
         20



         IO-



          0
                i     i    i    i     i    i    i     i    i    i    i     i    i    i     i    I     i    i  •

               2O   40  60  80   100  120  140  160  I8O 200 220  240  260 280  300  320 340  360

                                              DAYS OF OPERATION

                                Fig.-5 - CARBONACEOUS REMOVAL UNIT

                              PERCENTAGE OF WASTE UNDER TREATMENT

-------
The actual influent-to the carbonaceous unit was not monitored for quality
parameters.  Concentrations of cheraical constituents present in the in-
fluent were computed by multiplying the percentage of waste being treated
by the chemical quality of the undiluted excess ammoniacal liquor being
treated and tabulated in Table 5.  The computed influent qualities are
given in Table 8.  Any contribution to these constituents from the dilution
water is considered to be insignificant.  Plots of the influent concen-
trations of organic carbon and chemical oxygen demand are given in Figure 6-
phenolics, Figure 7;  thiocyanate, Figure 8: and ammonia and total nitrogen,
Figure 9.  The abrupt changes in concentrations to which the unit was
subjected are apparent from these Figures.

One of the purposes of this experiment was to determine under field
conditions the operating capabilities and limits of the biological
process.  In other words, more realistic design parameters were being sought
for the biological treatment of ammoniacal liquors than could be obtained
from small laboratory experiments.  For many wastes, design parameters
for treatment are often determined by conducting a series of experiments
using acclimated organisms in which temperature, pH, and viable organism
concentration are the major variables.  Ammoniacal liquor is a somewhat
unique waste in that, to date, raw liquor has never been treated success-
fully in a biological system without dilution.  Thus, the percentage of
waste becomes an important parameter also.  This additional variable
coupled with the unsteady quality of the raw waste already mentioned made
the experiment even more complex.

Host biological treatment experiments are monitored by computing a factor
called a loading parameter.  This term combines several operating variables
which often assists in understanding the observed behavior of biological
systems.  Several forms for the term exist but one which has proved to
be useful in explaining the results of laboratory studies can easily be
derived from a statement of mass balance for the system.  For a process
operating at steady state this balance may be expressed as (Mass in) =
(Ilass out) + (Mass reacted) .  Algebraically this expression becomes


            QCI = QCE + ft V
where
             Q = volumetric flow in the system,
            Cj = influent substrate concentration,

            CE = effluent substrate concentration,

             C = substrate concentration in the reactor,
             t = residence time in the reactor,
             V = volume of the reactor.
                                  58

-------
In
       1400


       I3OO-



       1200 -


       1100-


       1000-
     u
     - 9OOH
     O
     CD
8OO-


7OO-
u
u
z 600 H

o
CK
o 500 H
     ^400-

     u.

     -  300-


        200-


        IOO-


          O
                             ORGANIC
                             CARBON
          20  40
                       —T~

                        6O
                                         T
                                                    1
                     80  100  120  140
                  T	1——I	1	1	1	1—
160  ISO 200  220 24O 260  280 300 32O  340  360
DAYS OF OPERATION
                                Fig.-6- CARBONACEOUS REMOVAL UNIT
                           INFLUENT CONCENTRATIONS.ORGANIC CARBONaCOD
                                                                                                          evi
                                                                                                          O
                                                                                              - 8000 3.
                                                                                                    E

                                                                                              I- 7000 z
                                                                                                     6OOO Q
                                                                                                         z
                                                                                            - 5000
                                                                                                         >
                                                                                                         x
                                                                                                         O
                                                                                               4000 <
                                                                                                    u

                                                                                              - 3OOO u
                                                                                              -2000
                                                                                              -1000

-------
  2000-

  1800-
-i
z I6OO-

-------
  1200-


  1100-

  1000-


  900-
u
V)
^ 800
E
u 700
<
< 600
o
o
T 500
UJ
40O-

300-

200 -

 IOO -

  0
           i     i    i    i    i     I    *    i    i     i    i    *     *    i    i    i  •   Ir^
          20   40  60  80   100  120  140   160  180  200  220 240 260  280  300 320  340  360
                                        DAYS OF OPE RATION
                           Fia.-S- CARBONACEOUS REMOVAL UNIT
                         INFLUENT CONCENTRATION THIOCYANATE

-------
  4800-
  4OOO -
  32OO -
E 2400 -
z
UJ
o
o
a:
z  I6OO
   80O-
               40
 I        I         I         i        i
80       120      160      200      240
                 DAYS OF OPERATION
       Fig.-9-EXCESS AMMONIACAL LIQUOR
 CONCENTRATIONS TOTAL NITROGEN AND AMMONIA
28O
 I
320
 T
360

-------
For a complete-mix reactor as was used in this study, effluent concentra-
tions equal reactor concentrations  (C = CE).  In biological systems, the
rate of removal of substrate material is known to be proportional to
substrate and viable organism concentrations.  This may be stated as
            ft - KCS                                                (4)
where
            K = a proportionality constant and
            S = viable organism concentration in the reactor.


Substituting equation  (4) into equation  (3) and reducing yields


            QCCj - CE) = KCSV                                        (5)


But since V/Q = t, the aeration time in  the reactor, and Cj - CE = CR,
which is the concentration of substrate  removed, equation (5) reduces to
            C
            sf = KC


The left-hand term of  this equation defines the loading parameter.  An
arithmetic plot of this parameter versus  the effluent concentration of
substrate should provide a straight line  x\rith a slope equal to the pro-
portionality constant  K.  This derivation assumed constant temperature,
proper oxygen tension, appropriate pH  levels, satisfactory sedimentation,
and, in general, steady state operation.  The proportionality constant
will vary with all of  these and the results of the experiment will be
discussed in light of  these variables.

In the experimental approach utilized  to  determine the limiting loading
parameter possible in  the carbonaceous unit for the various substrates,
the system, after proper acclimation, was subjected to increased loadings.
System response was measured by monitoring the effluent and viable solids
concentration while maintaining a constant aeration time.  As loading
increases, a point is  reached beyond which system failure occurs.  This
failure may be manifested by an appearance of excessive amounts of sub-
strate or other constituents in the effluent.

A major problem with the use of equation  (6) is its failure to signify
whether the system is  not fully acclimated or is experiencing failure.
                                  63

-------
For example, in comparison to a system at steady rate, a system not
fully acclimated would show a low concentration of substrate removed and
a relatively high effluent concentration.  After failure, the identical
condition exists.  This deficiency may be overcome by modification of the
equation by converting it to an influent loading factor rather than one
based on substrate removal.  This modified equation becomes



            K • V,                                                m

where Y^ is a modified constant which may vary slightly with removal
efficiency.  This equation, although not as theoretically sound as
equation (6), does allow prediction of the particular mode in which the
unit is operating.  The influent loading parameter varies directly with
influent concentration.  At failure, this term will only reflect changes
in the concentration of viable solids in the reactor while the concen-
tration of substrate in the effluent will increase rapidly.

Values for this loading parameter are calculated and given in Table 9
for organic carbon, chemical oxygen demand, phenolics, cyanide, and
thiocyanate.  These loadings are based on the influent concentrations of
each constituent as computed and given in Table 8.  The reactor or aeration
time is constant for the entire experiment and is one (1) day.  The viable
solids concentration in the reactor is taken as proportional to the result
of the Imhoff cone reading on the mixed liquor.  This assumption may be
questioned on several points since the Imhoff cone technique measures the
volume of settleable solids and as such necessarily is influenced by the
settleability of the solids and does not differentiate between viable and
non-viable solids.  However, the advantages of this quick and simple test
conducted routinely for process control by the operator proved to be an
adequate substitute for more widely accepted measurements of viable solids.
The loading parameter calculated using this substitute for organism con-
centration will be utilized in subsequent paragraphs to explain operational
fluctuations.

In addition to the computed loading factor, the status of operation may
also be judged by other parameters including quality of the effluent in
terms of contaminant concentrations (Table 9), percentage removals of
contaminants (Table 9), effluent loads, and by changes in reactor solids
concentration (Table 7).  The purpose for the treatment of this waste is
to reduce the amount of contaminants in the waste discharge.  Since waste
discharge effect receiving streams on the basis of mass of contaminants
dishcarged, the concentration of a constituent multiplied by the volumetric
flow rate is important.  In the pilot plant, the flow rate was held con-
stant at one (1) gallon per minute so it can be neglected for comparative
purposes.  However, the plant was operated with a diluted waste and the
                                  64

-------
dilution factor becomes most important  in determining  the mass discharge
for a full-scale treatment plant.  For  example,  treatment of  25 percent
waste with an effluent concentration  of 10 mg/1  of  some  constituent dis-
charges a larger mass of material  than  one operating at  75 percent waste
and an effluent concentration of 25 mg/1.  Tabulations of effluent dis-
charge loads for comparative purposes for organic carbon, chemical oxygen
demand, phenolics, cyanide, and thiocyanate  are  given  in Table 10.

The carbonaceous treatment unit experienced  during  the operational period
of some 352 days several upsets or periods of  poor  operation.  Using the
parameters and factors just discussed,  the periods  of  smooth  operations
and problems will be discussed in  an  attempt to  derive guidelines for
design and operation of an ammoniacal liquor treatment unit.

The influent to the carbonaceous treatment units, for  the first 55 days
of operation, was only about 15 percent waste.   In  addition,  the waste
for the entire period was x*eak but was  especially so for the  first 40
days.  This combination of high dilution and weak waste  combined to pro-
vide a low influent loading.  However,  initially the concentration of
viable solids in the reactor was low  so the  influent loading  parameter
was high.  This, parameter decreased  rapidly as  the unit became acclimated.
On or about day 40, the strength of the waste  in terms of organic carbon
and phenolics almost doubled.  This was accompanied by a fall in reactor
pH resulting from partial nitrification of ammonia  within the carbonaceous
removal unit.  These changes were  reflected  in a decrease in  reactor
solids but the unit continued to operate most  satisfactorily  as measured
by percentage removals or mass discharge of  phenolics  and organic carbon.

The percentage of waste under treatment was  increased  to approximately
25 percent beginning on day 56.  This was reflected by a corresponding
increase  in influent loads for organic  carbon  and phenolics.  The system
was responding well.  Unfortunately,  on day  64 the  reactor temperature
was found to be 123° F, far too high  for this  type  of  treatment unit.
System problems produced poorer percentage removals of organic carbon
(93 to 71), presence of phenolics  in  the effluent  (124 mg/1), increases
in the amounts of  these two constituents discharged, and a sudden decrease
in reactor suspended solids.  Unit recovery  was  rapid  for both organic
cajbon and phenolics but required  almost two weeks  for suspended solids
concentrations to  increase substantially.

Corresponding to the sudden increase  in reactor  suspended solids came a
period of high influent organic carbon  concentrations.   The  initial part
of this period was also accompanied by  a reactor temperature  increase from
about 80  to 85° F  (days 82-91).  This short  period  was a time of excellent
treatment with waste percentage at about 40  percent,  low influent loading
parameters for organic carbon and  phenolics, removal  of  over  90 percent
of the organic carbon and  the best thiocyanate removal (88 percent) ex-
perienced during the entire test.
                                  65

-------
TABLE 10;   EFFLUENT LOADS PER UNIT VOLUME  OF WASTE
,

Period









1-5
6-13
14-21
22-29
30-39
40-43
44-48
49-55
56-57
58-60
61-67
68-73
74-76
77-81
82-84
85-88
89-91
92-95
96-98
99-103
104-108
109-112
113-116
117-121
122-129
130-136
137-143
144-150



Percent
Waste








13
15
17
15
15
16
16
15
22
29
23
27
25
24
36
42
38
47
61
64
57
70
76
73
82
89
56
65

Mass Discharged,
mg/1 per unit of waste
cs
H
CO
o

u u

c
CO
oo
s

250
180
180
130
120
140
100
130
110
120
630
170
180
280
180
200
170
120
250
80
250
90
60
120
160
300
70
40

c
0)
00
>. «N
° ,
f-l TJ
CO C
o to
•H 8
B a
01 Q
CJ



























1700
1200


*
CO
u
•H r-*
i-( O
§c
11
it f,
f* PU
PL,

0.8
1.3
1.2.
2.7
0.7
0.6
-
-
0
-
54.
0.7
-
0.3
-
0.5
-
2.1
-
0.2
0.4
-
0.3
7.0
0.7
0.7
0.5
0.3



„
o>
•o

a
tfl E5
^>U
O

5
6
4
6
7
13
21
13
6
11
7
4
6
12
14
8
7
8
9
12
8
14
26
7
9
8
9
8


0)
4J
s
to
;*>
u
OK
-H CJ

H

250
260
150
230
150
110
-
-
55
-
370
240
-
230
-
270
-
47
-
260
150
-
260
250
-
380
430
240



Period









151-157
158-164
165-171
172-178
179-185
186-192
193-199
200-206
207-213
214-220
221-227
228-234
235-241
242-248
249-255
256-262
263-269
270-276
277-283
284-290
291-297
298-304
305-311
312-318
319-325
326-332
333-339
340-346
347-352


Percent
Waste








60
54
49
72
78
74
74
74
86
71
68
79
81
75
40
17
23
43
47
58
30
22
35
45
45
58
49
46
47
Mass Discharged,
mg/1 per unit of waste
u
o
h
CO
o

o
•H

CO
oo
O
90





























0)
00
>> CM

^
rH ^0
to c
o to

e v
0 0
6
1200
1300
1300
1400
1000
900
1000
1400
900
2600
2600
3000
2600
3700
3900
3600
2700
1800
2300
2000
2200
1800
1400
1600
1600
1200
1300
1600
1600

-
•H rH
r-t O
O C3
C 0)
0) .C

p,


0.3
0.4
0.4
-
0.4
0.3
0.3
0.4
0.2
0.3
1.5
1.5
14.
21.
0.5
-
0.9
0.5
1.2
7.4
1.3
0.5
0.3
0.4
0.2
0.5
0.4
0.7
0.4


HI
•o

g
g"

u


14
7
8
7
7
7
8
7
4
6
7
6
8
7
9
10
9
11
10
17
10
12
12
13
14
9
9
11
11

M
QJ
iJ
S
CO



•^ C/3

H

270
310
350
-
240
340
300
370
160
380
570
1500
480
840
370
3000
960
440
620
530
470
820
710
620
620
480
570
630
600
                            66

-------
This short period was followed by a decrease in  reactor temperature by
almost 10° F over a period of about one week.  This may have accounted
for the appearance of phenolics in the effluent  (1 mg/1) and a decrease
in reactor solids.  Concurrently, the waste percentage under treatment
rose to about 60 percent which increased  loadings on the unit.

The period between days 99 and 116 was characterized by increasing waste
percentages being treated  (60 to 75), reactor  temperatures about 85° F,
good reactor dissolved oxygen concentrations,  and overall good removals
of major constituents.  The slow decrease in reactor suspended solids is
believed due to the increase in organism'activity resulting from increased
temperature.
                                         i
The system for the period  117-121 suddenly showed a phenolics concentration
of 5 mg/1 which was followed by a decrease in  reactor solids during the
next few days.  No definite reasons for  this system failure can be estab-
lished but certain observations may be significant.  Cyanide concentrations
in the raw waste, the unit's influent, and in  the effluent had been
increasing.  During the averaging period  just  prior to that of failure,
cyanide concentrations in  the reactor had increased from 10 to 20 mg/1.
In addition average reactor dissolved oxygen concentrations had decreased
from 4.1 to 2.8 mg/1.  The most plausible explanation probably involves
the presence of cyanide.

The period from 122-136 was characterized by low reactor suspended
solids and increasing percentages of waste treated.  The maximum per-
centage treated was 89 percent.  These two factors combined to increase
the influent loading parameters for organic carbon and phenolics.  Un-
fortunately, on day 136 the reactor-dissolved  oxygen concentration was
found to be only 0.2 mg/1 which is not considered an adequate level for
aerobic treatment.  Unit failure is indicated  by the low percentage re-
movals of chemical oxygen  demand and sudden reductions in reactor sus-
pended solids.

Operations during the interval between day 136 and 172 utilized between
50 and 60 percent waste and the waste during this period was moderately
weak.  The rather low influent loadings  along  with reactor temperatures
of almost 90° F combined to limit the reactor  suspended solids to low
levels.  Overall the interval was marked  by excellent removal of phenolics,
probably the best sustained removals of  cyanides, only fair removal of
chemical oxygen demand, but low mass discharge of COD.

Percent waste being treated x*as increased on day 172 from about 50 to 75
and was held at this level for about 75  days.  The first half of this
period was characterized by slowly increasing  influent loads of chemical
oxygen demand and phenolics.  Unit operation was comparatively steady up
until day 214 with temperature suspended  solids  at satisfactory levels.
Only occasional marginal dissolved oxygen concentrations were noted and
these apparently caused no major operational problems.  During this period,
the unit treated its highest waste concentration in which reactor foaming
was easily controlled.  Removals of phenolics  were excellent with removals
                                   67

-------
of COD and cyanide of about 60 and 70 percent, respectively.  Little or
no removal of thiocyanate was experienced which was especially disappointing.

On or soon after day 214 the strength of the raw waste in terms of chemi-
cal oxygen demand, phenolics, and thiocyanate suddenly increased by
factors of 1-1/2 to almost 4.  With essentially a constant percentage
of waste in the feed, the unit was subjected to a rather large change
in loading.  However, the unit continued to remove both COD and phenolics
although foaming in the reactor became a problem.  From the data, it
appears that the unit could have survived this shock loading.  Unfortunately,
however, the unit in the succeeding weeks was subjected to ever-increasing
loads and on at least day 223 to low dissolved oxygen levels and on one
day (228) reactor thiocyanate reached 1220 mg/1.  The units suspended
solids concentrations and its removal of chemical oxygen demand were
satisfactory.  Actually, only foaming and effluent phenolics concentrations
of about 1 mg/1 gave indications of problems.  A decrease in average re-
actor temperature from 90 to 78° F over the periods from days 228 to 248
caused major problems including loss of reactor solids and excessive ef-
fluent phenolic concentrations.

After unit failure, on day 249, the percentage of influent in the waste
was decreased in an attempt to restore performance.  Both phenolics and
chemical oxygen demand removals improved and from an effluent load view-
point the unit performed well.  The decrease in waste feed percentage was
accompanied by a decrease in the raw ammoniacal liquor concentration of
phenolics from over 2000 mg/1 to 650 mg/1 and although a corresponding
decrease in COD did not occur immediately, a trend to lower COD levels
in the raw liquor was established.  Reactor temperatures continued to be
low (minimum recorded was 61° F, day 289) until about day 300.  The most
notable problem during this period was the inability of the unit to accumu-
late organisms.  Treatment efficiency, as measured by effluent quality and
mass discharge for phenolics and COD were good.  The unit apparently x*as
acting essentially as an aerated lagoon.  The major differences between
a complete-mix activated sludge system and an aerated lagoon is that in
the lagoon no suspended solids are separated from the effluent and re-
turned to the reactor.  During this period, this unit operated on this
basis since little difference is noted in the concentrations of solids
in the mixed liquor and return sludge.  In other words, the return sludge
was the same as the mixed liquor.  This indicates a diffuse, growth which
settled poorly and contributed to turbid effluent as indicated by rela-
tively low Seechi disk readings during the oeriod.  This turbidity also
contributed to the effluent COD.  This ability of the system to operate
insofar as COD and phenolics are concerned as an aerated lagoon under
the adverse conditions of low temperature and at only a detention time
of 24 hours is most remarkable and should be pursued further.

Attempts to reconvert the system to an activated sludge regime included
reseeding of the system about day 260 without success and increasing the
reactor temperature around day 300.  This latter effort along with a
decision to operate the unit at a steady waste feed concentration of 50
percent brought about an almost immediate increase in reactor solids and
                                  68

-------
in sludge returned.  Phenolics removal continued to be  good and some im-
provement in COD is noted, at least part  of which  is due  to a less turbid
effluent.

In summary the carbonaceous removal unit  performed well during much of
the test period.  Several unfortunate occurrences  upset operation but
much was learned from  these disturbances.  Table 11 summarizes the opera-
tional parameters and  results during those periods of selectively stable
operation.  Treatment  of up to 75 percent raw ammoniacal  liquor was demon-
strated in a plant operating with an aeration period of 24 hours at tem-
peratures from 75 to 90° F.  Influent concentrations or organic carbon,
chemical oxygen demand, phenolics, and thiocyanate vary considerably from
period to period and do not vary in direct proportion to  the percentage
of waste under treatment.  This indicates the variability in the raw
waste under treatment.

Two interesting points concerning the loading parameter are x^orthy of
note.  First, levels of 4 to 5 for the organic  carbon factor at reactor
temperatures of 80 to  85° F appear to be  easily treated as judged by
percentage removals or organic carbon and phenolics as well as low mass
discharges for these constituents.  Neglecting  the period between 249
and 304, the influent  loading parameter for chemical oxygen demand appears
to be inversely related to the percent removal  of  COD.  Phenolics loading
parameters of around five did not cause problems.  The  second point of
interest is the period between 245-304 when comparatively large values
for loading parameters were encountered but reasonably  good treatment was
attained.  This apparently occurred when  the unit, probably because of
lower operating temperatures, began producing a diffuse biological growth
which did not settle.  The unit effectively became an aerated lagoon.
During this interval the mass discharges  of both phenolics and chemical
oxygen demand were somewhat greater than  when the  unit was operating as
an activated sludge unit.  However, the degree  of  treatment was surprising
considering only a 24-hour aeration time.

The removal of thiocyanate was most discouraging throughout the test.
The percentage removal of this constituent seems to decrease as influent
waste strength increases.  From some recent laboratory work, indications
that thiocyanate removing organisms are relatively sensitive and are
slow growers has been  found.  Thus, although some  suitable organisms
were originally present and became partially acclimated,  unit upsets
and loadings discouraged the development  of the thiocyanate organisms.
Removals of cyanide ranged from about 50  to 70  percent.   The reasons
for only partial removal of cyanide are not known  but it  is hypothesized
that the remainder is  in a form not amenable to biological oxidation or
air stripping such as  possibly a metallic complex  or organic compound.

Table 12 summarizes the failures which were experienced by the unit, how
the failure was recognized, and  the possible cause or causes of the
failure.  In all,  five major failures occurred  and caused varying degrees
of problems including  excessive  foaming in the  reactor; increases in
                                   69

-------
                        TABLE 11:   SUMMARY OF CONDITIONS DURING PERIODS OF UNIT STABILITY







Period






22-55
82-91
99-116
137-171
172-213
249-304
312-352
OPERATING CONDITIONS



01
4-1
CO
CO
:»
jj
c
o> "
o
H
0>
eu

15
40
70
55
75
35
50



fe
o
^
V
V.
3
4-1
CO
Vl
(1)
I-
01
H

80
85
85
90
90
75
90
INFLUENT

Concentrations,
mg/1


o
O "
•H a
c o
CO .0
00 fc
k CO
O 0

180
840
930
-
-
-
-

i
0)
«-l Q CM
CO O
u a
•H 01 •
S oo-o
v xc
43 X CO
uo e

-
-
-
1800
2200
2500
3000

A
ta
u
•r* t-4
i-l O
o c
C 01
01 X
4= P-.
Pk

100
350
500
330
550
370
570
o>
4-t
§
CO
>s
U Z
0 O
i-l CO
.C
H

40
230
150
180
220
210
310
Loading
1 1 ^
Parameterv '


u
•H C
a o
CO .0
00 l-i
jj CO
o y


4
5
4
-
•
-
-


r-l
CO C
U 0) *O
•* oo c
E >, co
Jg§
U Q


-
•
-
38
21
650
13

(0
u
••-i
i-H
O
c
01
FU


2
2
3
7
5
110
3
OPERATING RESULTS

nvsin fvtfvfnn n TTum j A T O
PERCENT REMOVALS
C
£>
M
3
u
•I-l
CO
00
M
O
88
92
92
-
-
-
«•



1-1
ce G
O *
o
O
•1-1
J3
H

50
50
30
30
15
10
10



01
•o
•r«
C
CO
>,
O '


45
55
50
65
70
,40
50
MASS ,.
T^T G/"*U A 'D/^C'C' V ^ /
DISCHARGES
C
o
JO
M
CO
U
0
•r-l
c
CO
00
M
O

120
180
120
-
-
-
-



^^
cdc
Udi*n
w w
•HOOC
g^>». M
p^TO
i«t c
?s t
J=O 0)
r 1 /"I
U t-4


-
-
-
1300
1100
2500
1500


(0
u
•H
i-4
0
C
0)
PH


1.0
.0.5
0.3
0.4
0.3
1.7
0.4
-J
o
     (!) See text for units..

-------
                        TABLE  12:    SUMMARY OF TREATMENT UNIT FAILURES
 PERIOD
           Manifestations
    Possible Causes
 61-67
 89-91
117-121
130-136
214-248
Reduction in % removal, organic carbon
Phenolics present in effluent
Increase in mass discharges
Decrease in reactor Suspended solids
\" J
Phenolics present in effluent
Decrease in reactor suspended solids

Phenolics present in effluent
Reduction in % removal, organic carbon
Increase, effluent cone., organic carbon
Decrease in reactor suspended solids

Excessive reactor foaming
Low,but unsatisfactory levels of phenolics
Low concentrations of reactor suspended solids
High reactor temperature,
     123°F, day 64.
Temperature decrease  accompanied
by increase in loadings.

High reactor cyanide levels,
up to 20 mg/1.
Decrease in reactor dissolved oxygen.

Low reactor dissolved oxygen.
Increase in load.
Large increase in load .
High reactor thiocyanate concentrations.
Low reactor dissolved oxygen,
intermittently.
Decrease in reactor temperature.

-------
effluent concentrations and reductions in percent removals of organic
carbon, COD, and phenolics; decreases in levels of reactor suspended solids;
and increases in mass discharges of COD.  These problems were caused by
increases and decreases in reactor temperature, sudden or large increases
in loadings, low reactor oxygen levels, and possibly high concentrations
of cyanide and thiocyanate.  In investigating these failures, not one
single case of failure resulting from slow increases in loading was
obtained.  Thus, maximum possible influent loadings were not necessarily
attained.
NITRIFICATION UNIT

The major nitrogenous component in excess ammoniacal liquor is ammonia.
In addition, there are smaller amounts of combined nitrogen in organic
compounds and thiocyanate.  As a result of nitrification in the carbonaceous
unit varying amounts of nitrite and nitrate may also be present.  In
addition to discussing the specific nitrogenous species, a term encompassing
all measured forms of nitrogen called total nitrogen is used.  Essentially,
total nitrogen, as used here, includes that present and measured as ammonia,
organic nitrogen, cyanide, nitrite, and nitrate.  Thiocyanate-nitrogen is
not included as a separate item because it is determined as part of the
organic nitrogen fraction.

The nitrogenous composition of the excess ammoniacal liquor utilized during
the pilot plant study is given in detail in an appendix and summarized in
Tables 5 and 6.  Figure 9 graphically presents the ammonia and total nitrogen
contents of the waste.  The total nitrogen curve is not continuous because
of insufficient data for all averaging periods for all of the components
which are included in this category.  As can be seen, the major nitrogenous
component by far is ammonia except for two consecutive averaging periods
near the end of the experiment.  For these periods, total nitrogen was
essentially divided equally between ammonia and organic nitrogen.  No
satisfactory explanation for this anomalous behavior has been found.  In
addition, note should be made of the sudden and large changes in ammonia
and total nitrogen content of the waste.  Changes by factors of abovit two
in the concentrations of these constituents apparently occur with some
regularity.

Some apparent removals of nitrogenous components and some interconversions
between the various nitrogen-containing compounds take place x-rithin the
carbonaceous removal unit.  Activated sludge plants treating municipal
sewage remove from 50 to 85 percent of the organic nitrogen fraction and
15 to 75 percent of the total nitrogen.  Nitrogen removals take place
by many mechanisms which include coagulation and sedimentation of colloids
containing nitrogenous components, especially organic nitrogen; volatili-
zation; and, incorporation into cell substance.  Interconversions between
forms result from the hydrolysis of organic nitrogen compounds to ammonia
and the oxidation of ammonia to nitrite and nitrate.  If the oxidation of
                                   72

-------
ammonia takes place, then the loss of nitrogen through denitrification is
also possible.  These same processes are operative  in the  treatment of
aramoniacal liquor in the carbonaceous removal unit.  According  to the infor-
mation given in Table 9, removals of ammonia in  the unit ranged  from 6 to
40 percent and averaged about 19 percent; total  nitrogen removal ranged
from 3 to 37 percent and averaged about 15 percent.  Unfortunately,
nitrite was not determined routinely on the effluent from  the carbonaceous
unit which casts some doubt on  the validity of these removals.   Further
discussion of this point will be given later in  this section.

The second stage of the pilot plant operation, the nitrification phase,
was started on January 8 and was initially fed ammonium sulfate  and
phosphoric acid in an attempt to develop a population of nitrifying
organisms.  On January 29, the  system was converted to a continuous feed
of one (1) gallon per minute of carbonaceous effluent.  This flow rate
represented approximately 24 hours of aeration time.  On February 1,
collection of routine analytical and operational data commenced  and the
ensuing discussion covers the period subsequent  to  this tine.

The operating conditions for the nitrification unit are given in Table
13 for averaging periods closely corresponding to those used for the
carbonaceous unit.  Special attention is called  to  those periods when
the unit was receiving carbonaceous unit effluent,  artificial ammonium
sulfate and water, and when a combination of the two was being treated.
The many changes between operating modes were made because of the varying
conditions of the carbonaceous  units effluent.   Most of the changes were
precautionary in that this unit ^as converted to artificial ammonia before
major changes in the carbonaceous unit were made.  This was done in order
to avoid possible upsets in the nitrification unit  resulting from sudden
changes in the carbonaceous unit's effluent.

The concentration of viable organisms in this unit  remained low  at all
times despite the fact that no  sludge was intentionally wasted.  This
was somewhat expected in view of the slow growth rate characteristics of
the organisms and their relatively poor efficiency  in converting inorganic
carbon compounds to cell bodies.  According to the  limited data  available,
mixed liquor suspended solids probably never exceeded 1,000 mg/1.  The
Imhoff Cone measurements indicate these low levels  also.  However, com-
parisons of the Irahoff Cone measurements between the mixed liquor and
return sludge point out that the settleability of the sludge was good
for most periods.  The Seechi Disk measurements  also indicate that the
effluent was reasonably clear and free of non-settleable solids.

A major factor of importance to autotrophic bacteria such  as the nitrifiers
is an available source of inorganic carbon.  This carbon can be  supplied
as carbon dioxide, bicarbonate, or carbonate.  These forms of carbonic
acid are interrelated through the ionization constants for the  acid and
the pH.  In natural waters, the quantities of these constituents can often
be estimated through the determination of alkalinity and pll.  Computations
                                   73

-------
13:
      OPERATING CONDITIONS NITRIFICATION UNIT




Period








2-6
7-14
15-22
23-30
31-40
41-44
45-49
50-56
57-58
59-61
62-63
66-69
70-74
75-77
78-82
83-85
86-89
90-92
93-96
97-99
100-102
103-104
105-107
108-115
116-121
122-130
131-137
138-144
145-151
152-156
157-158
159-165
166-172
173-179
180-186
187-193
194-200
201-207
208-214
215-221
222-228
229-235
236-242
243-249
250-251
252-256
257-263
264-270
271-277
278-284
285-291
292-298
299-305
306-312
313-319
320-326
327-333
334-340
341-347
348-352
Influent ,
Percent



01
3
O
u £
CO Q)
C 3
0 *-4
.Q UJ
(0 fj]
O
100
100
100
100
100
100
100
100
100
100
LOO

100
100
100
100
100
100
100


100
100

100





25
30
35
25



15





,j
(U
4j
n)













100







100
100


100

100
100
100
100
100
75
70
65
75
100
100
100
85
r-4
60

•a
i— 1
O
en
"O
a
•o
c
X.
tn
3
C/J

J
-•
















510
830
540
610
310
420
70
150


















o
41
3
n

u
Q.
£
H

82
81
81
83
83
79
82
82
82
83
85
86
90
93
91
94
96
86
85
90
94
91
88
92
92
89
95
95
95
95
95
96
96
95
96
95
95
96









x
a


6.9
7.1
7.4
6.9
7.3
7.3
6.9
7.2
7.1
7.0
7.4
6.6
6.5
7.3
7.1
7.1
7.4
7.2
7.9
8.3
6.8
8.2
7.8
6.8
7.8
8.0
7.1
6.9
7.3
8.0
6.4
6.9
6.9
7.8
7.5
6.6
6.7
8.1


PI
o
u
u
1?
M
4J
•f"*
c
•H

It
<
90
130
150
130
150
130
120
120
150
140
130
45
50
110
90
110
160
140
530
520
80
350
240
50
270
210
70
60
100
180
25
40
50
200
110
40
40
220

^-4
t
c
01
CO
x'
o
TD
>
1—4
o
Vt .
in
a
























3.4
3.1
2.6
2.0
3.0
2.9
2.7
2.0
2.5
2.6
3.0
3.3
3.1
1.7
1.9
Irohoff
cone , t
ml/1


g
3
cr
•r*
•J

•a
*

5
6
5
9
3
13
17
16
21
25
33
26
32
22
28
24
24
25
14
13
5
9
4
4
6
2
2
2
3
3
4
3
3
3
3
3
1
1

a
oo
•0
3
i— i
in

c

3
It
a:
8
10
15
20
28
28
43
44
47
66
57
63
39
58
56
50
54
30
25

13
17
7
8
12
3
4
6
7
6

8
11
5
7
4
3
5


(41
dj
_c
u
c
Vt
•**
Q
•*4
.C
U
U
Vj

4
3
4
5
8
8
10
6
5
6
5
9
9
6
5
5
5
4
5

6
7
5
10
4
7
10
16
20
18
11
11
9
5
9
10
18
9
Additives per period

pounds


-V.
^

E£
.2
•o
o









7
23
31
22
35
95

122
92
61




17


6
67
92

2
78
52

9




















































ml.
V
1
O
—
D-.
>— 4
's •
*J
3
.2
H











4
12
9
6.
4
16





















1
•u
u

.^
M
o


w
c
f






£




300








100




1650
400
1400
1400
1000
200



1300
1400
1200


14
14
12
12
14
z,
8
14
14
14
14
14
14
14
14
12
12
14
6
14
12
100
107
110
100
77
35
63
153
125
105
U
)4
80
74
122
97
41
107
90
46
38























40
1OO
80

40
30





































Comments


.


i
'-
,


















Temp. drop.
Alk. increase.







,


Jligli pH caused
by low 02-





























                    74

-------
based on this simple model would  indicate  large  amounts  of  inorganic
carbon present in the excess  ammoniacal  liquor.   However, in  the  case  of
this waste with its large concentration  of ammonia and pi! values  of
roughly 8.5-9.0 it can be easily  shown that the  apparent alkalinity as
determined is almost all due  to the  ammonia and  that  inorganic  carbon
levels are relatively low.  However,  in  subsequent treatment  stages when
ammonia concentrations, decrease either through treatment or dilution and
the pll decreases, the alkalinity  determination does become  a  measure of
the inorganic carbon content.  By reference to Appendix  A-2,  the  alkalinity
of the carbonaceous units effluent is seen to vary widely.  However, if
ammonia alkalinity is neglected,  the carbonaceous alkalinity  is normallv
only a few hundred parts per  million as  calcium  carbonate.  This  represents
only a small concentration of inorganic  carbon.   The  conclusion is quickly
reached that the waste cannot supply the necessary inorganic  carbon
directly and that this constituent must  be supplemented.

A possible source of inorganic carbon would be that produced  as consequence
of the oxidation of the organic carbonaceous material in the  first treat-
ment unit.  According to the  data in Table 5, the organic carbon  content
of the raw waste may be as high as 3,000 mg/1.   Unfortunately, even
though most of this is converted  to  inorganic carbon, the inorganic carbon
is mostly lost as carbon dioxide.  To prevent this loss  would require
pH values in excess of operational limits.  However,  conservation of
inorganic carbon is enhanced  by high pll  and every effort should be made
to operate this unit near the maximum operational pll.

Supplementary inorganic carbon has been  required in all  laboratory tests
as well as in the pilot unit  for  the nitrification of excess  ammoniacal
liquor.  Sources of inorganic carbon have  included limestone, calcium
carbonate, and soda ash.  Powdered limestone has worked  well  in the
laboratory but only limited experiments  were attempted in the field.
Sodium carbonate was used almost  exclusively because  of  its effectiveness
and ease of handling.  The addition  of inorganic carbon  to  an aerated
solution such as is encountered in the nitrification  unit can lead to  loss
of the carbon as carbon dioxide depending  upon the pH.   As  the  pH decreases
from 8, the rate of loss increases.   Since the nitrification  reaction  tends
to decrease the pll, control of this  parameter is necessary.  Several
chemicals including hydrated  lime, burnt lime, "and sodium hydroxide were
used for the purpose with sodium  hydroxide proving to be most suitable.
An attempt to provide a more  quantitative  view of the alkalinity  rela-
tionships in the nitrification unit  is given in  Appendix C.

Phosphoric acid was added to  the  unit during periods  when an  artificial
feed of water and ammonium sulfate were  being treated to supply the
biological process with the nutritional  necessity, phosphorus.
Phosphorus, during treatment  of ammoniacal liquor, was present  in the
effluent from the carbonaceous unit.   Tributyl phosphate was  occasionally
added as an antifoaming agent.
                                  75

-------
The basic purpose of the nitrification unit is to produce, nitrite and
nitrate from the incoming nitrogenous constituents.  Actually, the true
autotrophic nitrifiers are capable only of oxidizing ammonia.  However,
since no practicable way of limiting the biological activity of the
flora in this unit to the autotrophs was available, changes in other
nitrogenous constituents is also possible.  For these reasons, several
approaches to calculating the efficiency of the unit are available
and along with the operating results are summarized on Table 14.

Data for four periods are not included because of unsteady operations
resulting from changes between, carbonaceous effluent feed and artificial
ammonia feed in such a way that the changes could not adequately be
monitored.  In addition, one period was experienced when flow disruptions
occurred and the data obtained was not considered representative.  The
data for periods in which reasonable steady operation was experienced
is given.

The first several columns of Table 14 give the nitrogenous components
present in the influent to the nitrification unit.   These nitrogenous
components come from carbonaceous effluent and/or ammonium sulfate.
The effluent from carbonaceous unit was monitored for ammonia, organic
nitrogen which includes thiocyanate nitrogen, and nitrate nitrogen.
The "total" nitrogen listed as being contributed by this source is the
sum of these three components and unfortunately does not include nitrite.

When the unit was operating on 100 percent carbonaceous effluent, these
concentrations equal those given on Table 9 for the effluent from
carbonaceous removal.  When, according to Table 13, the unit was treating
a diluted carbonaceous effluent the influent nitrogenous concentrations
are computed using the appropriate percentage and the analysis of the
effluent for that period.

The computation of the concentration of ammonium sulfate in the influent
during those periods of its use are based on the flow of water and/or
waste and the weights of ammonium sulfate added per period as given on
Table 15.  Influent total ammonia and total influent nitrogen are the
sums of the respective constituents x-rithout regard to source.  Table 14
also gives a summary of the nitrogenous materials in the effluent from
the nitrification unit including ammonia, nitrite,  nitrate, total
oxidized and a total.  In this instance, organic nitrogen determinations
were not conducted.  As nitrite and nitrate are the designated end products
of this unit their concentrations are most important.

The purpose of this unit is to oxidize ammonia to nitrite and nitrate.
One way of judging this activity is to observe the amount of ammonia
removed.  A column for the percent of ammonia removal is given in
Table 14.  This indicates that removals up to 90 percent were experienced
at times but probably something like 60 nercent was more common.  Since
ammonia which passes this phase of treatment unoxidized will not be
                                 76

-------
                                                         TABLE lit

                                              NITRIFICATION UNIT. SUMMARY



PERIOD





2-6
7-14
15-22
23-30
31-40
41-44
45-49
50-56
57-58
59-61
62-74
75-77
78-82
83-85
86-89
90-92
93-96
97-122
123-130
131-137
138-144
145-151
152-158
159-165
166-172
173-179
180- 186
187-193
194-201
202-215
216-221
222-228
229-235
236-242
243-249
250-256
257-263
264-270
271-277
278-284
285-291
292-298
299-305
306-312
313-319
320-326
327-333
334-340
341-347
348-352
Nitrogenous materials, mg/1 as nitrogen
I n f 1 u
By source
Carbonaceous Effluent

CO
C
i
"*1
200
26O
240
220
200
210
200
230
280
410

600
950
1220
1260
1190
1290






500
540
520




460
580
670
410
580

130
190
310
400
470
220
200
270
400
440
280
210
190
420

c
fj Hi
•rJ QQ
n o
nj ij
ao *j
0 Z
30
30
30
20
20
20


20
-

-
50

40
-
60






.30
50





30
40
40
20
20

-
20
20
20
20
20
20
10
10
10
100
230
230
20

c
01 V
^* 00
CO O
hJ It
z z
o
0
0
1
70(''
90(U
60
70
60
70

CM
\^
CO
0
H
230
290
270
240
290
320
-

360
-
e n t



•" &
U VI
ifci CM
*J '•J
U X
< Z
0
0
0
0
0
0
0
0
0
0




=p
ca C
ij O
O E
H E
200
260
240
220
200
210
200
230
280
410



CM
^ C
at
-< oc
CO o
0 u

230
290
270
240
Effluent




c
o
e

190
220
170
160
2W(-1' 120
320<1) 160


360

230
220
220
310
Oxidized


a
%
Z
z
40
48
56
61
77
69
69
76
110
127



4J
OJ
i^
£
40
53
71
70
89
87
91
108
87
114



_
2
o
H
80
100
130
130
160
150
160
180
200
240



c**
CO
w
!*
270
320
300
290
280
330
390
400
420
550
INTERMITTENT USE OF ARTIFICIAL AMMONIA ADDITIONS
1
5
6
5
5
7

1010
-
1310

1360
0
0
0
0
0
o
600
950
1220
1260
1190
1290
-
1010

1310

1360
190
710
610
740
550
660
230
215
185
344
396
192
103
182
115
348
441
214
330
400
300
690
840
410
520
1110
910
1430
1390
1070
INTERMITTENT USE OF ARTIFICIAL AMMONIA ADDITIONS




0
0
0
O
320
230
430
430
320
230
430
430
320
230
430
430
210
50
120
50
3
67
156
230
4
64
145
200
7
130
300
430
220
180
420
480


_
O

COS
V
(JfB
we
RJ O
I

5
15
29
27
40
14
-

21
24

68
25
50
41
54
49

34
78
72
89
INTERMITTENT USE OF ARTIFICIAL AMMONIA ADDITIONS
0
0




530
590

0
0
0
0
0
0
230
210
210
5OO
540
520
230
210
210
530
590
-
230
210
210
230
330
1000
200
120
70
F L 0 « DISRUPTION AND pH PROBLEMS
0 . 490
0
0
0
0
620
710
430
600
0
0
0
0
0
460
580
670
410
580
INTERMITTENT
0 . - 360 490
0
0
0
0
0
0
0
0
0
0
0
0
0
210
330
420
490
240
220
280
410
450
380
440
420
440
330
110
160
170
210
210
220
10
0
0
0
0
0
520
420
560
640
430
410
490
410
440
280
210
190
420
490
620
710
430
600
190
330
380
250
240
149
135
46
25
49
41

101
210
241
257
227
112
138
40
26
37
37

103
176
188
221
288
260
270
90
50
90
80

200
390
430
48O
510
490
600
1090
250
210
150

390
720
810
730
750
54
39

13
43
67

59
42
43
39
59
USE OF ARTIFICIAL AMMONIA ADDITIONS
-
540
440
580
660
450
430
500
420
450
380
440
420
440
50
130
150
510
400
110
70
110
80
190
50
140
360
470
326
267
152
0
0
0
154
263
210
140
222
209
62
127
366
335
189
58
83
128
201
197
204
131
243
231
112
171
690
600
340
60
80
130
350
460
410
270
460
440
170
300
740
730
490
570
480
240
420
570
490
460
510
580
530
770
90
75
64
10
37
75
83
78
80
58
82
33
-



C "D
Cu CU
a N
C ?
U X
o
0 C
cw
4J Ofi
C O
a> t*
o w
a»
30
31
43
45
57
46
41
45
48
44

64
36
33
48
60
38

3
72
72
90

53
45
8
20
43
53

51
54
53
66
67

93
82
69
10
17
54
83
81
84
59
90
76
32
40


?
C
y
00
o
.,4

CO
O
H
250
310
330

290
330
310
290

_

_
300
.
550
_
560

320
230
430
430

61O
650
-
230
210
210

580
740
850
710
780

-
580
520
660
720
490
430
570
500
510
460
530
480
450


c
oo
*
z «
O
C
01
CJ

-------
         TABLE
                   OPERATING CONDITIONS, DENXTRIFICATION UNIT
(Influent  *  constant  I gpm of nitrification effluent unless  noted)


Period








3-7
8-15
16-23
24-31
32-41
42-45
46-50
51-57
58-59
60-62
63-75
76-78
79-83
84-86
87-90
91-93
94-97
98-123
124-131
132-138
130-145
146-152
153-159
160-166
167-173
174-180
181-187
188-194
195-202
203-216
217-222
223-229
230-236
237-243
244-250
251-257
258-264
265-271
272-278
279-285
2 86- 2 02
2<)3-20s
4J

B
•14
f_4
n
J£
<
140
230
180
270
350
300
370
400
440
580

•^
tf
8
BO
1

T3

r-l
o
w
to
O




2.6





Imhofr
Cone,
nig /I
k<
o
3
cr

J

-a
0
X
S
19
38
29
23
5
4
3
2
2
0>
00
•o
3

(/!

C
k4
3
01
od
35
40
40
48
7
5
3
3
5
6 ' 7

to
0)
JS
2
•*4
M
at
•H
a

>r4
.£
U
U
w
5
4
4
3
4
5
3
3
2
2

X
1
s<

A


O
1
0
GQ



2
2





USE OF ARTIFICIAL
360
380
420
290
440
840





1
2
4
2
0
3
4
8
1
1
3 ' 3
4
3
3
3
2
3






I1 S T OF ARTIFICIAL'
230
390
470
510
470
520
480
390
260
340
190
-
0.1
0.8
".1
0.6
0.2
0.2
1.1
u.O
0.0
0.2
2
1
1
1
1
0

1
3
5
3
5
•y
4

2
1

3
3
12
1
2
3
4
4
4
4
-
3
3
4
4












Special
Problems





00
c
t4
E
4
f\
S















y
a
•r4
M
r-4
.3
CO


X
X
X






|
b

u
C
V
3
U4
c
M



X


X




i
16 2














X

X





X
X
V





I T 2
•^ Dark color, bad odor.







X

































Intermittent molasses flow.






L1 s F ;> F A R T I F i c I A i MI, i :: u :: T 2
030
1080
980
350
510
560
620'
850
870
680
830
780
3»«"" SS-AvR.
115mg/l.
i
!


                                      78

-------
removed by later stages of treatment, the low percentage obtained limits
the overall removal potential for the plant.  However, the plant was not
operated to produce a consistent effluent because of the many variations
in treatment schemes used in both the nitrification and carbonaceous
units.  Therefore, more normal operation should be expected to approach
the maxima rather than the average obtained in such an experiment.
Fairly steady operation for the periods near the experiments end possibly
indicate that 75 to 80 percent ammonia removal might be anticipated.
Another way of looking at the operation of the nitrification unit is to
compute the percentage of the effluent nitrogen that is oxidized.
According to the column so labeled, values ranging from less than 50 to
more than 90 percent were experienced.  Since only oxidized nitrogen
is capable of removal in the denitrification unit, the percentage
oxidized places an automatic upper limit on plant efficiency.  Again,
values approaching the maxima should be expected under steady plant
operations.

Careful scrutiny of Table 14 for the amount of nitrogen in and out of
the unit shows that in practically all cases when carbonaceous unit
effluent is being used, apparent nitrogen increases occur within the unit.
Nitrogen imbalance is expected in biological systems but not in the
form of consistent increases.  The easiest and most straightforward
explanation is to assume that some oxidation of ammonia to nitrite is
occurring in the carbonaceous unit.  This is martially borne out by the
excellent balances obtained for the onlv periods, 31-40 and 41-44, in
which nitrites in the effluent were determined.  An additional indication
is the frothing noted intermittently in the clarifier of the carbonaceous
unit often caused by denitrification.  If this is accepted as the
explanation, then the apparent nitrogen removals reported for the carbon-
aceous unit may not be real.  In addition, if this is true, then 'a
nitrogen balance across both the carbonaceous and nitrification unit
should be of interest.  The last two columns of Table 14 provide this
information.  The total nitrogen here is computed from the influent
values of total nitrogen for the carbonaceous unit as given in Table 8
and the percentage of carbonaceous effluent fed to the nitrification
unit is given in Table 13.  The nitrogen balance in terms of percent
lost is inconsistent but varies around zero.  This variation around
zero is taken as evidence that little or no change in total nitrogen
content occurs within the first two treatment units.  Thus, the criteria
of effluent nitrogen oxidized definitely nlaces the upper limit on the
overall plant ability to remove nitrogen either on the basis of percentage
or absolute removals.  The percentage of effluent nitrogen (roughly
equal to plant nitrogen inputs) oxidized has been discussed.  This
parameter along" with the absolute amount of oxidized nitrogen produced
will be utilized to define periods of stable and unstable operations.

The first sixty days for the nitrification unit consisted of onerating
directly on the effluent from the carbonaceous unit.  During this
period, the carbonaceous unit was treating only a 15 percent dilution
of a relatively weak ammoniacal liquor.  Operation was not ontiraum,
however, because of low reactor temperature.  The response of the
                                 79

-------
nitrification unit to this effluent was slow but steady improvement in
the amount of nitrogen oxidized and in the percentage of influent
ammonia oxidized.  The amount of ammonia removal within the unit remained
low and probably indicates that most of the nitrification is taken place
within the underloaded carbonaceous unit.

Just as increases in waste loads under treatment were being made, an
unfortunate failure of the temperature control equipment for the
carbonaceous unit took place and resulted in failure of that unit
accompanied by transfer of poorly treated waste to the nitrification
unit.  This resulted in a drastic decrease in the quantity of nitrogen
oxidized by this unit and indicated impending failure.  To provide the
nitrification unit with an ammonia feed during the interval required
for recovery of the carbonaceous unit, intermittent use of synthetic
feed was practiced until day 75.

The unit was returned to carbonaceous effluent feed on day 75.  This
action was accompanied by a change in reactor temperature to about
90°F.  During the first week of this interval, the influent ammonia
concentration increased from 600 to 1,200 mg/1 which represented the
maximum concentration of ammonia received by the unit during the entire
test.  The period between days 82 and 91 was also marked by the excellent
treatment of 40 percent waste by the carbonaceous unit.  The nitrifica-
tion unit responded to all these factors by producing rapidly increasing
effluent concentrations of oxidized nitrogen.  During one sampling
interval, effluent oxidized nitrogen increased by almost 150 mg/1    per
day.  This was the maximum observed rate of increase and may give some
indication of the response time of the unit to changes in the influent
characteristics.  Unfortunately, before steady state conditions were
established, and just as improving percentages for removal of ammonia,
ammonia oxidized, and effluent nitrogen oxidized were becoming apparent,
the carbonaceous unit again became upset.

A sudden decrease in the temperature of the carbonaceous unit accompanied
by increasing loadings in the periods folloxtfing day 90 subjected the
nitrification unit to a poorer quality effluent including phenolics of
about one mg/1 for a short interval.  In addition, this problem vras
accompanied by a decrease in nitrification unit temperature (96 to 86°F)
and the combination resulted in a sudden decrease in nitrification
efficiency.  This unit failure was followed by a period from days 97 to
122 of unsteady operation and feed.  During this period, the carbonaceous
unit again experienced problems and the unit x
-------
The decision was made, however, that the carbonaceous effluent would be
diluted prior to being applied to the nitrification unit.  The purpose
of this dilution was to reduce and dampen fluctuations in the quality
of carbonaceous effluent resulting from operational changes in that
unit.  Unfortunately, three days prior to the conversion (day 152)
the nitrification unit, while still on artificial feed, was subjected
to a pH of 9.9.  Analyses of samples taken the  following day indicated
a decrease in nitrification.  However, before all of the ramifications
of the units condition were known, the unit was converted to diluted
waste.  The unit did not respond and was returned to artificial feed
on day 180 without success.

Following a time of treatment disruptions resulting from mechanical
problems, the unit was again placed on a feed of diluted carbonaceous
effluent on day 216.  This time the unit responded slowly and showed
a steady improvement in nitrified nitrogen.  During this interval
reactor temperatures of about 90°F and pH values around 7 were
experienced.  On day 249, after about two weeks of poor quality
carbonaceous effluent, the nitrification unit was placed on intermittent
synthetic feed to avoid upsetting this unit.  On day 257, after improve-
ment in the carbonaceous unit, the nitrification unit began receiving
an effluent supplemented by artificial ammonia.  Upon resumption of
treatment the unit apparently had no ill effects from the transition.
Oxidized nitrogen levels as well as percent ammonia oxidized and effluent
nitrogen oxidized v?ere all at or near maximum possible levels.

This period of excellent performance was followed by a period which
extended to the end of the experiment in which  reactor temperatures
were low, mostly in the low to middle eighties.  This period can be
subdivided into two parts based on influent feed.  The first part, from
about days 260 to 310 consisted of a diluted carbonaceous effluent plus
artificial ammonia.  Unit response was not satisfactory.  The combination
of low reactor temperature plus a relatively poor carbonaceous effluent
resulting in high loadings of chemical oxygen demanding materials
including phenolics may have been responsible.

The  second part of this period, from about day  315 to the experiment's
conclusion, utilized only diluted carbonaceous  effluent without supplemen-
tal  ammonia.  This effluent was much improved in quality over that of
the  preceding period.  The nitrification unit responded well, especially
in light of the low reaction temperature, by providing several short
periods in which excellent nitrification occurred and in which 75 to 90
percent of the nitrogen was nitrified.

A major problem with the entire nitrification experiment was that condi-
tions were never stable enough for a period of  sufficient length  to
allow establishment of a steady state.  In biological systems, variation
almost invariably leads to less than optimum performance.  Good
nitrification was obtained most consistently only when the carbonaceous
unit was operating in a satisfactory manner.  In addition, best nitrifi-
cation was obtained at reactor temperatures of  90 to 95°F with relatively
                                 81

-------
poor nitrification at 80 to 85° F.  Unit failures or problems resulted
mostly from carbonaceous unit failures.  One failure was caused by a
high reactor pH 9.9.  The optimum pH range appears to be about 6.8 to
8.2.

An attempt to outline a reaction mechanism for the nitrification unit
including an alkalinity balance computation is given in Appendix C.
DENITRIFICATION UNIT

Denitrification is the major function of the third treatment stage.  As
outlined previously in Section V, denitrification is the process in
which nitrate and nitrite nitrogen is biochemically reduced to nitrogen
gas with the concurrent oxidation of organic matter.  Denitrification
thus has the potential for converting potential nitrogenous contaminants
into an inert form.

The denitrification system was placed on line January 29, 1970, and
initially received one (1) gallon per minute of nitrification unit
effluent.  This flow represented a reaction time of approximately 8
hours.  Detailed surveillance of the influent and effluent began with
the first averaging period in February which began for this unit on the
third because of the two 24-hour detention periods in the preceding
treatment stages.

Tables 15 and 16 provide summaries of the operating conditions and
operating results for the denitrification unit.  More detailed information
may be found in the Appendix.  Being the last of the three units, the
denitrification reactor was subjected to all of the fluctuations either
encountered or resulting from the previous treatment stages.

Table 15 gives the summary of the major operational parameters measured
routinely during the test of the denitrification unit.  Essentially the
only control exercised over this unit was through the amount of
reducing agent added.  During roughly the first one-fifth of the
experiment, sucrose sugar was used while in the remainder of the experiment,
molasses was used.  The amounts of these materials added are given for
each period in the first two columns.  As with all biological processes,
temperature and pH are important, but no control over these parameters
was exercised in the denitrification unit.  Temperature within the reactor
varied from a low of 71 to a high of 93°F.  This variation would be
expected to influence greatly the rate of denitrification.  The pH
and alkalinity increase as a result of the overall denitrification
process.  Values of pH as high as 9.2 and alkalinity increases of up to
almost 1,000 mg/1 as CaC03 were experienced.  Dissolved oxygen concentra-
tions approaching one mg/1 were encountered during the experiment without
apparent disruption of denitrification.
                                   82

-------
The denitrification process depends upon the availability of organisms
capable to utilizing oxidized nitrogen in their metabolic processes.
The use of the Imhoff Cone to measure the concentration of these organisms
in this unit was less than adequate.  First, the Imhoff Cone measurement
depends upon sedimentation of the organisms and denitrifying sludges,
instead of settling, often tend to float because of entrapment of
released nitrogen gas.  An additional complication resulted because,
without doubt, some biological growth took place because oxygen entered
the system through the surface of the stirred reactor.  Despite these
complications, there is some evidence from the data to suggest that
Imhoff Cone readings do correlate with the- degree of denitrification.
Limited suspended solids measurements indicate low biological levels.
No routine blowdown from this unit was made.  Slowdown actually occurred
through the discharge of a turbid effluent resulting from poor sedimenta-
tion of this particular sludge.  Low Seechi Disk readings confirm the
turbid nature of the effluent.

The operational problems encountered by this unit included, in addition
to mechanical problems such as influent flow and sludge return disruptions,
a bulking sludge on occasion.  The bulking nature of the sludge made
mandatory a surface skimming device to collect sludge from the
sedimentation compartment for return to the reactor.

The major operational function of the denitrification unit is to reduce
the nitrite and nitrate formed in the preceding treatment units to
nitrogen gas using an added reducing agent.  Obviously, the nitrite and
nitrate concentrations in the influent and effluent are important
operational parameters and are tabulated in Table 16.  Since one of the
functions of the three-stage plant was the overall removal of nitrogenous
matter, ammonia and total nitrogen concentrations are also given.

The organic content of the effluent is a most important operational
factor.  The origin of this material may be either the residual not
removed in the two preceding treatment units or that intentionally added
as either sugar or molasses.  These quantities are entered in Table 16
in terms of chemical oxygen demand.  To assist in judging the efficiency
of the treatment unit, percent losses or removals of ammonia, oxidized
nitrogen, total nitrogen, and chemical oxygen demand are also listed.

The removal of ammonia is not a  function of this unit and losses of
this component were not expected to be large.  Small losses may be
accounted for by incorporation into the sludge.  Actually, as can be
seen from Table 16, in many of the periods ammonia increases within the
unit are noted.  Since ammonia removal is one of the primary objectives
of the treatment scheme, any increase in ammonia is undesirable.  Several
possible reasons exist for this observation.  The worst possible case
would be the reconversion of nitrite and nitrate by denitrification into
ammonia rather than nitrogen gas and organisms are known which are capable
of this.  Unfortunately, if this were the case, nothing would be
accomplished by the nitrification and denitrification treatment steps.
                                  83

-------
The non-consistent nature of the gains and losses in ammonia cast some
doubt on this explanation.  More careful examination of the operating
ponditions existing during periods of gains and losses of ammonia pointed
out an interesting correlation.  With only a very few exceptions, ammonia
gains are noted only when artificial ammonia is being added to the
nitrification unit and only losses occur when the nitrification unit is
entirely on waste feed.  The best explanation for this observation appears
to be purely an operational one rather than biological.  During times
of artificial ammonia additions to the nitrification unit, slugs of
ammonia sulfate were added once per day.  This meant that ammonia
Concentration in the effluent varied with time.  In addition, the
amount in the effluent from the denitrification unit x^ould also vary.
Since samples for ammonia were collected simply by grab techniques, the
observed results could easily be obtained.  However, when all units are
treating waste waters, there is no slug effect as all systems are running
gmoothly and concentrations of constituents do not change rapidly.  At
any rate, during periods when waste is being treated and since this is
the time of maximum importance, small losses of ammonia, possibly
ranging to 10 or 20 percent, might be expected within the denitrification
stage.

The major change expected within this unit is the decrease in the
content of oxidized nitrogen.  Oxidized nitrogen losses of greater than
95 percent occurred with some regularity during the test.  Considering
the lack of consistency in the preceding treatment steps, these results
indicate that the denitrification unit is capable of performing its
intended function.

The loss of total nitrogen in the unit is not an effective measure of
the efficiency of the denitrification treatment unit alone, but rather
pf the nitrification and denitrification unit combined.  For the most
part, only the nitrification unit can treat ammonia and the only
nitrogenous materials capable of sizable removals in the denitrification
tin it are oxidized forms.  Thus, only with both units operating at peak
efficiency will good overall removals of nitrogen be obtained.  Unfor-
tunately, the nitrification unit seldom oxidized more than 75 percent
pf its effluent nitrogen.  This means that for most of the time at least
?5 percent of the nitrogen passing on to the denitrification unit was
tmoxidized.  For practical purposes, 75 percent removal of total
nitrogen is an upper limit even with 100 percent effectiveness of the
denitrification stage.  Actual losses approaching 70 percent x^ere
Pleasured for some averaging periods.

The reduction of oxidized nitrogen by the use of artificial reductants
Such as sugar or molasses needs careful control.  Only with control
can the proper stoichiometric quantity be added that will supply just
enough reductant to reduce the oxidized nitrogen content adequately
without providing an excess that will not be oxidized and thus pass
                                84

-------
                                    TABLE 161.   OPERATING RESULTS.  DENITRIFICATION UNIT


J



3-7
8-15
16-23
24-31
32-41
42-45
46-50
51-57
58-59
60-62
fcl 7 1
D J / J
76-78
79-83
84-86
87-90
91-93
94-97
QD 1 O*3
yt> i*. j
124-131
132-138
139-145.
146-152
153-159
160-166
167-173
174-180
181-187
168T194
195-202
203-216
217-222
223-229
230-236
237-243
244-250
251-257
258-264
265-271
272-278
279-285
286-292
293-299
300- 306
307-313
314-320 .
321-327
328-334
335-341
342-348
349-352
INFLUENT


z


190
220
170
160
120
180
230
220
220
310
190
710
610
740
550


Z
1
(U
•ft
z

40
48
56
61
77
69
69
76
110
127
N T E


z
0)
Nltrat

40
53
71
70
89
87
91
108
87
114
DMT
230 103
215
185
344
396
660 192
T N T F B
L B 1 C. I
210 , 3
50
120
50
67
156
230
182
115
348
441
214
;M T T
H ,L J
4
64
145
200
CONCENTRATIONS, mg/1
"S
N
V Z
S c
X «l
O 00
4J -r<

80
100
130
130
160
150
160
180
200
240
TT F
X I*
330
400
300
690
840
410
TF K
& r
7
130
300
430

z
^ 1
-* c
• 00
4J U
r =

270
320
300
290
280
330
390
400
420
550
NT 1
J. L
520
1110
910
1430
1390
1070
TIT
U
220
180
420
480
COD, as 02
e
o
.H
•J u
n c
11 01
itrifli
Efflui
BE









Ic F
D &




SP r
fc t.

220
300

c
HI
IncreoH
Added

380
210
210
210
300
380
380
380
380
380
01? i
e f
330
330
260
330
330
330
F*
A
660
660
660
660


Total


-
-

-
-
-
-
-


-






880
960
EFFLUENT

Z
id
•H
C


170
210
170
140
100
150
170
210
180
290
140
630
980
740
530
890
410
120
180
110

z
i
Lf
U
*4
Z

23
2
33
8
17
0
0
0
0
0
11
130
92
260
410
190
0
13
21
100
INTERMITTENT USE OF ARTIFICI
230
33O
1OOO
200
120
70
149
135
46
25
49
41
112
138
40
26
37
37
260 490 340
270
90
50
90
80
600
1090
250
210
150
350
490
90
80
80
MAJOR FLOW PR
190
330
38O
250
240
101
210
241
257
227
103
176
188
221
288
200
390
430
480
510
390
720
810
730
750
400
570
650
620
650
660
660
660
660
660
660
1000
1010
1150
750
74O
740
0 B t E M S
660
660
660
660
660
1060
1230
1310
1280
1310
200
310
960
360
170
110
14
8
0
0
0
13
E N C 0 U N
150
300
370
250
170
12
7
31
70
70
CONCENTRATIONS, mg/1

z
V
z

24
2
40
11
20
1
1
2
1
1
Am.
M
82
110
58
260
330
200
A M M
0
17
69
91
A L t
15
6
0
0
0

T E R
10
6
25
74
103
«
S
ll
00
•-* o
CO Id
82

50
5
70
20
40
1
1
2
1
1
M/*l **
U N
90
240
150
520
740
390
ONI
0
30
90
190
M M (
30
10
0
0
0
30
E D
22
10
60
140
170
INTERMITTENT USE OF ARTIFICIAL AMMONI
50
130
150
510
400
110
70
110
. .80
"190
50
140
360
470
326
267
152
0
0
0
154
263
210
140
222
209
62
127
366
335
189
58
83
128
201
197
204
131
243
231
112
171
690
600
340
60
80
130
350
460
410
270
460
440
170
300
740
730
490
570
48O
240
420
570
490
460
510
580
530
770
510
500
430
280
300
360
430
420
440
360
450
470
360
340
1000
1000
10OO
1000
850
660
660
900
1000
1000
1000
1000
850
1000
1510
1500
1430
1280
1350
1020
109O
1320
1440
1360
1450
1470
1210
1340
90
170
140
530
470
150
100
130
80
160
50
130
470
460
86
4
18
0
0
0
38
29
19
0
26
26
1
0
105
7
16
0
0
29
32
32
15
0
27
31
2
0
190
10
30
0
0
30
70
60
30
0
50
60
3
0
z
t
c
OJ
00
0
k<
«J
o
H
270
240
270
180
160
190
-
240
210
III n
A A
900
1190
-
1330
-
A At
420
170
290
320
N I A
260
350
-
380
190
150

200
350
600
440
720


-------
through the plant and degrade effluent quality.  Reductants,  as
measured by the chemical oxygen demand and mentioned previously,  are
either residual organlcs resisting removal in the previous  treatment
steps or artificial additions of sugar or molasses.  The  losses or
utilization of the total chemical oxygen demand is given  as a percentage
of total input to the system in Table 16.  These values for the most
part vary between 40 and 60 percent.  The removals are low  in part,
because of the refractory nature of much of the COD.  The utilization
of added COD materials which are not refractory is given  in the last
column.  Percentage losses for COD on this basis approaches 90 percent
in some tests.

The most critical aspect of the operation of the denitrification  unit
is the determination of the amount of reductant necessary to  result in
removal of the oxidized nitrogen without having an excess.  This  amount
of reductant can be estimated in several ways.  Stoichiometrically, the
amount can be computed based upon assumed oxidation-reduction reactions
and measured concentrations of nitrite and nitrate.  These  computations
for the last three months of the test are given in Table 17.  The
concentrations of oxidants, nitrite and nitrate and reductants as
measured by chemical oxygen demand both in and out of the unit are
reproduced from Table 16.  The following derivations allow  the
conversion from concentration units to milliequivalents per liter (meq/1)

            (1)  Nitrite to nitrogen gas
            Thus,
                     2NO~ + 8H+ + 6e
                     meq/1 (NO ')  - _3 C
                                     14
where the electron (e"~) change per mole or equivalents per mole of nitrite
equals 3 and there are 14 grams of nitrite-nitrogen per gram molecule.
C    - is the concentration of nitrite in mg/1 as nitrogen.


            (2)  Nitrate to nitrogen gas

                     2NO~ + 12H+ + lOe"
            Thus
                     meq/1 (NO ~)  -  _5 CMn-
                                      14  N°3
                                   86

-------
                                     TABLE  17;
DENITRIFICATION - STOICHIOMETRIC COMPUTATION
Period
279-285
286-292
293-299
300-306
307-313
314-320
321-327
328-334
335-341
342-348
349-352
OXIDANTS
Nitrite
In
mg/1
0
0
0
154
263
210
140
222
209
62
127
Out
mg/1
0
0
0
38
29
19
0
26
26
1
0
Change
mg/1
0
0
0
116
234
191
140
196
183
61
127
meq/1
0
0
0
251
50
41
30
42
39
13
27
Nitrate
In
mg/1
58
83
128
201
197
204
131
243
231
112
171
Out
mg/1
0
0
29
32
32
15
0
27
31
2
0
Change
mg/1
58
83
99
169
165
189
131
216
200
110
171
meq/1
21
30
35
60
59
68.
47
77
71
39
61
Total
Change
meq/1
21
30
35
85
109
109
77
119
110
52
88
REDUCTANTS
Chemical Oxygen Demand
In
mg/1
1280
1350
1020
1090
1320
1440
1360
1450
1470
1210
1340
Out
mg/1
1070
1020
640
500
580
580
730
630
690
670
660
Change
mg/1
210
330
380
590
740
860
630
820
780
540
680
meq/1
26
41
48
74
93
108
79
102
98
68
85
Error
Ox .-Red.
meq/1
- 5
-11
-13
11
16
1
- 2
17
12
-16
3
%
of
Reductants
19
27
27
15
17
1
3
17
12
24
4
oo
-J

-------
            (3)  Chemical Oxygen demand

                 The COD reaction in terms of oxygen can be
                 written as
            Thus,

                      meq/1 (COD)  -    C
                                         COD
Using these equations, the change in milliequivalents per liter of
nitrite, nitrate, and chemical oxygen demand between the influent and
effluent of the unit were computed.  Since, on an equivalent basis,
oxidations must equal reductions, the difference or error should be zero.
Actual errors, for those averaging periods shown in Table 17, are as
high as 17 meq/1 and up to almost 30 percent.  Computations of the same
parameters for less uniform operating periods show even larger errors.
The fact that the computed errors show excesses of oxidants during
some periods and almost equal excesses of reductants during others
tends to indicate that no consistent error was incorporated into the
reaction theory.  In other words, the reactions proposed fit the
experimental data as well as could be expected.  The errors may well
result simply from the unsteady nature of the operation and the use of
grab samples.  In addition, the changing efficiencies in the separation
of the organisms in the sedimentation tank due to sludge bulking and
other factors can have a large effect on the chemical oxygen demand of
the effluent and in turn on the redox balance.

All in all, the theory proposed agrees with that found in the laboratory
experiments and that proposed by others, and this data tends to varify
its validity.  On this basis, it is assumed that the major reduction
reactions occurring within the denitrification unit are the formation
of nitrogen gas from nitrite and nitrate and that the simultaneous
oxidation involves converting organic carbon to carbon dioxide.  The
latter reaction can be monitored easily through the use of chemical
oxygen demand measurements.  The dosage of organic reducing agent needed
for denitrification can then be computed in terms of COD for various
nitrite and nitrate concentrations by the following equation:

                      n     *c  fi(   c      4-    p     ^     i
                      "COD     °44 ^NO, -   14 LNO, -'
                                       £           O

where D n  s stoichiometric COD dosage in mg/1,
       COD
            CNO  - * nitrite concentration in mg/1 as N, and


            CNQ  _ » nitrate concentration in mg/1 as N.
                                  88

-------
This stoichiometric computation may be used as a first approximation
of the required amount of reducing agent to convert the oxidized
nitrogen forms to nitrogen gas.  However, this computation assumes
that the reaction will go to completion without excess reagent being
present.  Data, as given on Table 16, indicates that during the best
period of operation, 91 percent of the added chemical oxygen demand
was oxidized while 97 percent of the oxidized nitrogen was lost.

Several other tests indicate that 90 percent of COD and 95 percent
loss of nitrogen should be possible with proper analytical and operational
controls.  The total amount of COD necessary in terms of mg/1, TCQ_, then
would equal



            TCOD  "  8'9  (14 CN02 - +  14
The concentration  of  COD in the effluent would be  the residual
passing  through  the nitrification unit plus  an amount approximately
equal  to 10  percent of TQQQ.   The effluent would also be expected to
contain  about  5  percent of the oxidized nitrogen in  the influent to
the denitrification unit.
                                   89

-------
                          SPECIAL STUDIES
During the course of this investigation, several special projects were
conducted to enhance the understanding of aramoniacal liquor treatment,
to extend treatment capabilities, to investigate use of supplementary
treatment steps, and to reduce treatment costs.  These studies of most
interest were concerned with the carbonaceous treatment unit and develop-
ment of alternate methods of denitrification.
CARBONACEOUS UNIT

The treatment of ammoniacal liquors for removal of carbonaceous materials
has been repeatedly demonstrated.  However, the treatment has only been
accomplished with considerable difficulty and with less than optimum
results in some instances.  For example, the waste must be diluted prior
to treatment and thiocyanate has been difficult to remove.

Near the end of the experimental phase of this project, a pretreatment
step was proposed that reportedly made the waste more amenable to bio-
logical treatment.  This proposal was made by International Hydronics
Corporation, and reference is made to this under the authors' names, W.
G. Cousins and A. B. Mindler, in Section V,  Essentially this pretreat-
ment process consists of free and fixed ammonia distillation at pH 11,
followed by addition of spent pickle liquor for both neutralization and
coagulation.  Following sedimentation, the waste is reported to be more
easily treated.

The laboratory modification of the proposed pretreatment step was to
treat a batch of excess ammoniacal liquor with lime to a pH of 11 and
to heat this mixture to approximately 93°C.  Aeration was then applied
to strip ammonia to any desired level.  After cooling, synthetic spent
pickle liquor consisting of one percent free hydrochloric acid and 6
percent ferrous iron was added to chemically coagulate the liquor and
to reduce the pH of the waste to about 9.  After sedimentation, the waste
was ready for treatment in the experimental unit!.  Typical percentage
reductions in some of the major components as a tesult of the treatment
are given in Table 18 for an excess ammoniacal liquor from a coke
plant in the Pittsburgh, Pennsylvania, area.  As can be seen, this treat-
ment procedure results in a considerable change in some of the major
waste constituents, especially cyanide.
                                 91

-------
TABLE 18:  PRETREATMENT OF EXCESS AMMONIACAL LIQUOR, PERCENT REMOVALS
                          Aeration    Coagulation only,   Aeration and
Constituent               only          no aeration        coagulation
Chemical oxygen
Thiosulfate
Sulfide
Organic carbon
Phenolics
Ammonia
Cyanide
Thiocyanate
25
25
20
20
15
—
80
0
20
20
10
10
10
0
90
0
30
35
30
25
20
—
90
0
The treatability of this waste x
-------
TABLE 19:  BIOLOGICAL REMOVALS FROM PRETREATED ,WASTE
                                       Pretreatment Procedure
                           Aeration  &  Coagulation        Coagulation only
                             Cone., mg/1     percent      Conc.^mgA   Percent
   Constituent               Inf.   Eff.     Removal     Inf.   Eff.   Removal
Ammonia, N.
Phenolics, phenol
Organic carbon, C
Thiocyanate, SCN
Chemical oxygen demand, 00
500
1700
2000
960
7100
-
2
700
920
2800
-
99+
65
5
60
4000
1400
1900
1100
6800
-
3
800
1100
2900
-
99+
60
0
55
 The difference betx
-------
consisted of a 10 percent dilution of excess amrnoniacal liquor whose
pH had been adjusted to about 7 and to which phosphate had been added.
At this dilution, the influent contained about 140 mg/1 of phenolics
and 105 mg/1 of thiocyanate.

Operating with an aeration time of 24 hours, after five days over 90
percent removal of phenolics was noted but no thiocyanate was removed.
Under past operating criteria, waste strength would have been increased
based on phenolics removal; but since in this instance thiocyanate removal
was paramount, influent loading was maintained.  It was not until day 12
that thiocyanate removal was noted.  On that day, about 50 percent removal
was noted, and on the following day over 99 percent was lost.  The influ-
ent waste concentration was then slowly increased in steps with careful
monitoring of the effluent for phenolics and thiocvanate.  After each
incremental increase, both phenolics and thiocyanate would normally be
present in the effluent in low concentrations with phenolics disappear-
ing before the thiocyanate.  After a few failures of the system, it was
determined that with this particular ammoniacal liquor, only about 25
percent x^aste could be treated in the test unit and obtain consistent
removals of thiocyanate of better than 90 percent.  The maximum concen-
tration of thiocyanate treated under these conditions was about 300 mg/1
with effluent levels of about 10 mg/1.

After the conclusion was drawn that the limiting concentration of this
excess ammoniacal liquor that could be processed in the test unit for
thiocyanate removal was 25 percent, the unit was converted to coagulated
waste feed.  The use of pretreated waste allowed the use of 50 percent
waste concentrations to be utilized by the unit, and to maintain thiocyanate
removals.  Thiocyanate levels as high as 525 mg/1 were reduced to 20 mg/1
during periods of optimum operations.

In summary, for laboratory units utilizing a 24-hour aeration time and
room temperatures, treatment for phenolics removal was possible at a
maximum waste concentration of 60 percent.  This waste, with pretreat-
ment, could be treated for phenolics removal without dilution.  Thiocyanate
removal frpm this same waste was only possible at a waste concentration
of 25 percent and with pretreatment, this maximum was increased to 50
percent.

Chemical studies of the reaction products of the thiocyanate sulfur indicates
that about one-half is converted to sulfate with no sulfide, sulfite, or
thiosulfate.  The exact fate of the other half was not determined but
elemental sulfur is suspected.

DENITRIFICATIQN UNIT

Sizeable quantities of reducing agent are needed to satisfy the demands
of a well-nitrified ammoniacal liquor in the denitrification process.
The use of either sugar or molasses for this purpose is expensive and
alternatives were sought.  Among the alternatives given consideration
were the use of ferrous iron, the raw waste itself, and municipal sewage.
                                   94

-------
The use of ferrous iron,  a well-known  chemical  reducing agent, for the
treatment of coke plant wastes  appears to be  an optimum solution consider-
ing that the steel industry  also  produces sizeable  quantities of wastes
containing ferrous iron.  A  report  by  Gunderloy, e£ al. (65) proposes
the use of ferrous iron specifically for denitrification.  Numerous
attempts by the laboratory staff  to reproduce the results reported or to
denitrify wastes were unsuccessful  as  most  all  of the  oxidized nitrogen
reduced could be accounted for  as nitrite or  ammonia.  After consider-
able testing, this alternative  was  abandoned.   '

Another potential alternative for a source  of reducing agent was the
waste itself.  The wastes capacity  for reduction is measured by its
chemical oxygen demand.   Several  operational  schemes are possible in
which great savings  in air requirements and neutralizing chemicals can
accrue if raw waste  can be treated  using nitrite and nitrate as oxidizing
agents.  Unfortunately, denitrification could not be initiated using
atranoniacal liquor as the  reductant  even though  much care and patience
was exercised.

A last possibility considered was the  use of  the nitrified effluent from
the second stage of  the  treatment scheme  to oxidize or treat municipal
wastes.  Many  (see Section V) have  shown  that oxidized nitrogen can be
used as a substitute for  some of  the  oxygen required to satisfy the car-
bonaceous oxygen demand of domestic wastes.  As an  example of the po-
tential of this process,  let it be  assumed  that the excess ammoniacal
liquor has an  ammonia concentration of 4000 mg/1.   In  addition, assume
that one-half  of the ammonia is nitrified to  nitrite and the other to
nitrate.  According  to equations  developed  in Section  VIII, this amount
of nitrite and nitrate will  equal about 1150  milliequivalents per liter
for the reaction to  nitrogen gas.  The non-settleable  chemical oxygen
demand of a municipal waste  is  estimated  to be  about 200 mg/1.  In terms
of milliequivalents  per  liter,  this is 25.  This means that for a stoichio-
metric reaction  the  flow  of  municipal  waste would  need to be almost 50
times the flow of  ammoniacal liquor.   In  other  words,  100,000 gallons of
a well-nitrified ammoniacal  liquor could  satisfy the entire carbonaceous
oxygen demand  of 5 million  gallons  of  domestic  sewage.  The savings in
denitrification  cost to  the  coke  plant and  aeration capacity to the
municipal treatment  plant are obvious.
                                     95

-------
                             SECTION X
                          COST ESTIMATES
In this Section estimates of the capital and operating costs of a
biological system designed to remove nearly all of  the phenol and
ammonia from excess ammonia liquor are developed.   Other contaminates
such as C.O.U., cyanide  and thiocyanate will have smaller percentage
removals.  The costs developed here are not intended as firm estimates
for an actual treatment  system.  Rather, they are the most probable
costs based on available but incomplete technology.  The basis for
the estimates is a scale-up of the pilot system used in this study.
As described in previous sections, numerous problems were encountered
during the operation of  this system.  Many of these problems were
solved during the course of the study but others went unresolved.
Additional development work will be required to define the unanswered
questions before the system can be considered for full scale application.
This development work may have a substantial impact on the actual costs.
For this reason, the following estimates should be  used only for
evaluating the need and  potential return of further development work.

A coke plant producing 33,000 tons per month (TPH)  was selected as
the basis for the cost evaluation.  This size system is representative
of a large number of existing coke plants in this country.  With only
minor adjustments, the costs developed here should  be applicable to
many existing facilities.  In those cases where scale-up or scale-dox^n
is necessary, it is recommended that the logarithmic method frequently
used in chemical engineering be employed to adjust  the capital cost.
This method is expressed as follows:


                         Cn = rXCe
where Cn is  the new plant  cost,  Ce  is  the  estimated  cost from this
report, r  is  the  ratio  of  new waste volume to  40,000 gpd, and x is
the scaling  factor.  A  value  for x  of  0.65 is  suggested.

The production of 33,000 TPH  coke from coal with  5 percent moisture
will result  in the discharge  of  approximately  40,000 gallons per day
(gpd) of excess ammonia liquor.   Typically this waste will contain
6000 ppra (2000 Ibs/day)  C.O.D. and  4000 ppm (1350 Ibs/day) NH--N.
It is assumed that this waste will  be  diluted  to  50  percent strength
(80,000 gpd) before treatment in the carbonaceous removal unit.  The
carbonaceous removal unit  effluent  will then be diluted to 25 percent
strength (320,000 gpd)  prior  to  treatment  in the  nitrification and
denitrification units.  At these dilutions 80  percent C.O.D. removal
and 95 percent removal  of  NH3-N  is  expected.   The capital cost of
the three  stage treatment  system designed  to handle  this waste volume
is estimated at $995,000.   This  cost is for a  battery limits plant
located on a developed  site.   A  breakdown  of the  estimate  is given  in
Table 20.
                                     97

-------
          TABLE 20:   CAPITAL COST E.A.L.  BIOLOGIC AT, TREATMENT
  I.   CARBONACEOUS REMOVAL UNIT

      E.A.L.  Storage Tank
      Aeration Tank
      Clarifier
      Surface Aerator
      Transfer Pumps  (2)
      Sludge  Recycle Pumps  (2)
      Phosphoric Acid Feed
      Antifoam Feed
      Sludge  Drying Bed
      Structural Steel
      Piping  and Valves
      Electrical and Instrumentation
 II.   NITRIFICATION UNIT

      Aeration Tank
      Clarifier
      Surface Aerators  (2)
      Sludge Recycle Pumps  (2)
      Sodium Carbonate & Lime Ai
      Structural Steel
      Piping and Valves
      Electrical and Instrument.
III.  DENITRIFICATION UNIT

      Mix Tank
      Air Flotation Tank
      Mixers  (2)
      Sludge Recycle Pumps
      Molasses Addition
      Structural Steel
      Piping and Valves
      Electrical and Instrumentation
DESIGN
CRITERIA
48 hr. det.
24 hr. det.
350 gpd/ft2
2.5 Ibs. 0,/hn hr
2

1 1/ra gal E.A.L.
67 ml/m gal E.A.L.



:tion
Sub Total
24 hr. det.
350 gpd/ft2
2.5 Ib. 02/hp hr.
200 gpra
idition


it ion
Sub Total
8 hr. det.
700 gpd/ft2
0.1 hp/m gal.




it ion
Sub Total
:OTAL DIRECT COSTS
INDIRECT COSTS
?OTAL PROJECT COST
UNIT
SIZE
80,000 gal
80,000
20 ft dia.
40 hp
30 gpm
60 gpm
10 gpd
1 gpd





320,000 gal
35 ft dia.
45 lip






110,000 gal
25 ft. dia
6 hp
200 gpm









COST
$ 21,000.
27,000
30,000
11,000
2,000
,4,000
10,000
10, '000
15,000
12,000
35,000
50,000
$227,000
$ 73,000
53,000
24,000
6,000
30,000
15,000
40,000
50,000
$296,000
$ 36,000
53,000
10,000
6,000
15,000
15,000
40,000
50,000
$225,000
$748,900
$247,000
$995,000
                                      98

-------
The costs presented in Table 20  are based on scale-up of  the pilot
plant described in Section VI.   To solve some of  the operating problems
encountered during the pilot study, four modifications to the original
design were made.  Excess ammonia liquor storage  was increased from 24
hours to 48 hours to provide more cooling and equalization.  The system
was designed for gravity flow between  treatment modules to eliminate
the transfer stations.  Caustic  addition to the nitrification unit was
replaced with separate systems for the continuous addition of lime and
soda ash.  And, the denitrification unit final clarifier  was converted
to an air flotation system to eliminate biological solids losses from
sludge bulking.

The operating cost of the system is estimated at  $230,500 per year.
This estimate reflects current steel industry costs for materials,
utilities, and labor.  A breakdown is  given in Table 21.  For a
33,000 TPM plant, the unit treatment cost is $15.78/1000  gallons.
In terms of production, this is  an increase of $0.58/net  ton coke.
If it is assumed that production cost  above initial coal  cost is
$7.00 per net ton, biological waste treatment would represent a cost
increase of about 8.7 percent.

In evaluating the operating costs, two items warrant further dis-
cussion.  First, it was assumed  that hydrated lime and sodium carbonate
would be used in the nitrification unit for pH control and a source of
inorganic carbon.  There are a number  of compounds or combinations of
compounds that could be used to  supply these requirements.  A cost
comparison of four possible chemical systems is given in  Table 22.
As shown, the limestone system is  the  most economical from a chemical
cost standpoint.  The requirements for handling larger tonnages of
limestone and increased amounts  of waste sludge resulting from unreacted
limestone outweigh the cost advantage, however.   For this reason, the
sodium carbonate-hydrated lime system  was selected as the most practical
method of pH control and source  of inorganic carbon.

The second item is the use of molasses as a source of organic carbon
in the denitrification unit.  This carbon requirement could be
supplied with a variety of materials.   Almost any organic compound
which is water soluble and biodegradable could be used.   The economics
of several materials were evaluated during the study.  A  summary of
the evaluation is given in Table 23.   Molasses is the least expensive
of the materials considered.  For  this reason, it was used for the
cost evaluation.  In some parts  of the country, however,  molasses may
not be available.  In these areas organic carbon  costs should be
developed around methanol.  This is the most economical alternate
and a material that has been reported  successful  in denitrification by
numerous investigators.
                                   99

-------
          TABLE 21:  OPERATING COST BIOLOGICAL TREATMENT
                   Operation:               3 turns/day, 365 days/year
                   Waste Volume:            40,000 gpd E.A.L.
                   Fixed Investment:        $995,000
DIRECT COSTS                        UNITS/YR.       $/UNIT      $/YR.
                                                                 •y  '
  Materials:
      Molasses                       700 Tons          24      17,000
      Sodium Carbonate               600 Tons          50      30,000
      Hydrated Lime                  720 Tons          20      14,400
      Phosphoric Acid  (75%)          20 Tons         226       4,500
      Tributyl Phosphate  (100%)    1.18 Tons        1170       1,380

  Utilities:
      Steam                    55,000 mm Ibs.      $ 0.75      41,000
      Water                      100 mm gals.       20.00       2,000
      Electricity                1.10 mm kwh         0.01      11,000
INDIRECT COSTS

      Operating Labor               4 man          15,000      60,000
      Maintenance Labor and Material       5% fixed cost       49,220

                               Total Operating Cost          $230,500
                               (Excluding Interest and Depreciation)
             Unit Operating Costs:     $15.78/1000 gala. E.A.L.

                                       $0.58/Ton Coke
                                  100

-------
                 ^
           Waste Volume:        40,000  gpd E.A.L.
           Ammonia - Nitrogen:  4000 ppm  (1350#/day)
                                MI1S/YR._      I/UNIT
              *
Limestone Only
      Crushed Limestone         3070  Tons         12       $  36,800

Soda Ash Only
      Granular Sodium  Carbonate 1630  Tons         50       $  81,000

Soda Ash and Caustic
      Granular Sodium  Carbonate   600  Tons         50         30,000
      Liquid (50%)  Sodium Hydroxide
                                1550  Tons         50         77,500

           TOTAL                                           $225,300
Soda Ash  and Hydrated Lime
      Granular  Sodium Carbonate  600 Tons         50        30,000
      Pox^dered  Calcium Hydroxide 720 Tons         20        l^'J^L
            TOTAL                                           $ 44,400
                                  ,101

-------
    TABLE 23:  COST COMPARISON OF ORGANICS FOR DENITRIFICATION
           Waste Volume:        40,000 gpd E.A.L.
           Ammonia - Nitrogen:  4000 ppm (1350#/day)
                          THEORETICAL^
                         REQUIREMENTS
                                          UNITS/YR.    $/UNIT
                        $/YR.
Sucrose                      2.59
Formaldehyde                 2.59
Methylethylketone (MEK)      1.'24
Acetone                      1.30
Methanol                     1.90
Molasses                     2.85
640 Tons
640 Tons
305 Tons
320 Tons
468 Tons
700 Tons
220
216
210
118
 82
 24
141,000
136,000
 64,000
 38,000
 38,000
 17,000
          ft
           Assuming 50% as nitrate and 50% as nitrite.
It is apparent from the estimates developed above that the biggest
percentage of the cost for biological treatment is ammonia removal.
Seventy percent of the capital cost and 80 percent of the operating
cost can be directly attributed to nitrification and denitrification.
The phenol removal system represents only 30 percent of the capital
and 20 percent of the operating costs.
                                   102

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                            SECTION XI

                         ACKNOWLEDGEMENTS


The laboratory and field studies  reported herein were  carried out
by representatives of Armco Environmental Engineering  and  the Water
Resources Fellowship at Carnegie  - Mellon University.

The staff of the Water Resources  Fellowship  sponsored  by the American
Iron and Steel Institute are  recognized for  their very important role
in performing laboratory studies  and  evaluating pilot  plant data.
Special recognition is given  to Dr. William  R.  Samples formerly Senior
Fellow and Head of the Water  Resources  Fellowship,  for his generous
assistance without which this project could  not have been  completed.

Mr. J. E. Barker and Mr. R. J.  Thompson of Armco Environmental
Engineering are recognized  for their  contributions  in  directing and
coordinating the research and development effort on the project.

Mr. William Chadick and other representatives  of the Houston Works of
Armco Steel Corporation are recognized  for their contributions and
cooperation during the course of  the  study.

The partial financial support of  the  study by  the American Iron and
Steel Institute and  the EnvironmentaLProtection Agency is hereby
acknowledged.
                                    103

-------
                             REFERENCES
                             — -• --F -.-•-—I•- IIBII -MT« _!• - , f


 1.  "Reducing Phenol Wastes from  Coke  Plants",  Compiled by  the Steel
     Industry Action Committee  of  the Ohio  River Valley Sanitation
     Commission,  Cincinnati, Ohio,  January,  1953.

 2.  Barnes, Thomas H,  Albert 0. Hoffman, and H.  W. Lovnie,  Jr.,
      Evaluation  of Process  Alternatives to  Improve Control  of Air
     Pollution from Production  of  Coke", Battelle Memorial Institute,
     Columbus, Ohio, January 31, 1970.

 3.  Black, H. H., G. N. McDermott,  C.  Henderson, W. A. Moore, and H. R.
     Pahren, "Industrial Waste  Guide -  byproduct  Coke," Journal of the
     Water Pollution Control Federation, 1956, 494-527.

 4.  Samples, William R.,  "Fate of  Phenolics in  Coke Quenching", Mellon
     Institute Report,  Carnegie-Mellon  University, Pittsburgh, Pa., 22
     July 1969.

 5.  Samples, William R.,  Unpublished Data, Mellon Institute, Carnegie-
     Mellon University, Pittsburgh, Pa.

 6.  Rudolf's, Willem,  Industrial Wastes. Reinhold Publishing Corporation,
     New York, 1953.

 7.  Renkin, W. 0., "Ammoniacal Liquor  Clarification Process", Communica-
     tion to Water Resources Fellowship, Mellon  Institute, July 25, 1949.

 8.  "Phenol Wastes Treatment by Chemical Oxidation", Compiled by The
     Steel Industry Action Committee of the Ohio  River Valley Water
     Sanitation Commission,  1951.

 9.  Rhodes, E. 0., "German  Low-Teranerature Coal-Tar Industry", Informa-
     tion Circular 7490, U.S. Dept. of the Interior, Bureau of Mines,
     February, 1949.

10.  Blackburn, W. H., "The  Effluent Problem of the Gas and Coking
     Industries", J.Institute of Sex* a Re Purification, 199-207 (1958).

11.  Ackeroyd, B. A. and G. W. J. Bradley, "Effluent Purification at the
     Avenue Carbonization and Chemical Plant of the National Coal Board",
     Air and Water Pollution in the Steel Industry, The Iron and Steel
     Institute, London, 1958.

12.  Arthur D.  Little, Inc., "A Study of Coke-Oven Ammonia", (AISI),
     March 9,  1961.
                                    105

-------
13.  Siewers, H. et_ ai., "Process for Destroying Ammonia Contained in
     Water Resulting from the Operation of Coke Ovens", U.S. Patent
     3,540,189, November 17, 1970.

14.  Private Communication ("lichael Perch) September 27, 1966.

15.  Private Communication (R. E. Iluder) October 27, 1966.

16.  Rosenblatt, E. ?. and J. 0. Cohn, To Baher Co., Inc., "Dissociation
     of Ammonia", U.S. Patent 2,601,221.

17.  Samples, W. R., "Lira!tins the Output of Ammonia from Coke Plants
     and Steel Mills", Mellon Institute, Pittsburgh, Pa.

18.  Hcliichael, F. C., "Ammonia Decomposition and Oxidation", Mellon
     Institute, Pittsburgh, Pa., February 1969.

19.  Vigani, F., "A Literature Review of Ammonia Synthesis and Decomposi-
     tion by Catalysts of Iron", Mellon Institute, Pittsburgh, Pa.,
     February 1969.

20.  Temkin, il. I. and Pyzhev, V., ACTA Physiochem., USSR, 12, 327 (1940).

21.  Emmett, P. II. and Love, K. S., J. Araer. Chem. Soc., 63, 3297 (1941).
     "The Catalytic Decomposition of Ammonia Over Synthetic Ammonia
     Catalysts".

22.  White, A. II. and Melville, W. , "The Decomposition of Ammonia at High
     Temperatures", J. Amer. Chem. Soc., 27, April 1905, p. 373-336.

23.  Thomas, Charles L., "Catalytic Processes and Proven Catalysis".

24.  British Patent 746,697, February 17, 1954, "Process for Destroying
     or Preventing the Formation of Ammonia During the Coking of Coal".

25.  Hill, William H., "Recovery of Ammonia, Cyanogen, Pyridine, and Other
     Nitrogenous Compounds from Industrial Oases, "Mellon Institute,
     Pittsburgh, Pa. (1942).

26.  Wilson, Philip J. and Wells, J. H., "Coal, Coke and Coal Chemicals",
     McGraw-Hill Book Company, Mew York, 1950.

27.  Dean, R. B., "Nitrogen Removal from Wastewaters", Paner No. 5
     "Removal of Ammonia by Selective Ion Exchange", F.W.Q.A. , Cincinnati,
     Ohio, May 1970.

28.  ilercer, B. W., ejt _al_. "Ammonia Removal from Secondary Effluents by
     Selective Ion Exchange", Battelle-Northwest, October 5-10, 1969.
                                    106

-------
29.  Harvey Rosen - Project Manager,  Pollution  Control  System.  W. R.
     Grace & Co., Davison  Chemical  Division, Baltimore, Ilarvland,
     January 21, 1971.                                     "

30.  Eliassen, R. and Tchobanoglous,  G.,  "Removal  of Nitrogen and
     Phosphorous from Wastewater",  Environmental Science and Technoloev
     3., No. 6, June 1969.

31.  Frauson, F. and O'Farrell, T., "Ammonia Stripping  at Washington,
     D. C.", U.S. Dept. of the Interior,  Federal Water  Pollution Control
     Administration, Univ. of Pittsburgh,  Nutrient Removal Seminar,
     February 17-18, 1970.

32.  itcMichael, F. W. Samples and F.  Vigani, Report on  the Removal of
     Ammonia from Industrial Wastewater Streams by Air, Appendix A,
     llellon Institute, Pittsburgh,  Pa., February 1969.

33.  Eliassen R. and Tchobanglous,  G., "Removal of Nitrogen and Phosphorous
     Compounds from Wastevrater", Environmental Science  and Technology,
     JJ, No. 6, June 1969,  p. 536-541.

34.  Nusbau, I., J. Sleigh, Jr., and  S. Kremen, "Study  and Experimenta-
     tions in Wastex^ater Reclamation  by Reverse Osmosis", Feder Water
     Quality Administration, Uept.  of the  Interior, May 1970.

35.  Young, G. R., H. R. lungay, L. M. Brown, and  W. A. Parsons, J. Water
     Pollution Control Federation,  395-398  (1946).

36.  Gunderloy, Frank C.,  Cliff Y.  Fujikawa, V. II. Dayan, and S. Gird,
     "Dilute Solution Reactions of  the Nitrate Ion as Applied to Waste
     Water Reclamation", U.S. Dept. of the  Interior, FWPOA, Cincinnati,
     Ohio, October 1968.
      f
37.  Chao, Tyng-Tsair and  Wybe Kroontje, "Inorganic Nitrogen Transforma-
     tions Through the Oxidation and  Reduction of  Iron", Proceedings
     Soil Science Society  of America, 30.  193-5 (1966).

38.  Rudolfs, Willem, Industrial Wastes, Reinhold  Publishing Corporation,
     New York, N.Y. (1953).

39.  Frankland, P. F., and Silvester, H. J., J. Soc. Chem. Ind., 2^t No. 6,
     231-7 (1907).

40.  Fowler, G. J. and Holton, A. L., J. Soc. Chem, Ind., .30, 180-8, (1911),

41.  Key, A., "Gas Works Effluents  and Ammonia," London, Institution of
     Gas Engineers (1938).
                                    107

-------
42.  Brown, Ralph L., U. S. Patent 1, 437, 394 (1922), assigned to the
     Koppers Co., Inc.

43.  Mohlman, F. W. , Am. J. Pub. Health. 19_, 145-56 (1929).

44.  Mohlman, F. W., Sewage Works J.. jL9_, 473-7 (1947).

45.  Mathews, W. W., Sewage and Industrial Wastes, 24, No. 2,164-30
     (1952).

46.  Iluller, J. M. and Coventry, F. L., "Disposal of Coke Plant Wastes
     in Sanitary Sewer System," Presented to the Western States Blast
     Furnace and Coke Plant Association, Chicago, Illinois, January 19,
     1968.

47.  Morgan, H. H., Knudson, C. II. and Swaney, W. A., "Destruction of
     Phenols in Ammonia-Still Waste," United States Steel Corporation,
     Pittsburgh, Pennsylvania (1954).

48.  Kostenbader, P. D. and Flecksteiner, J. W., Journal Water Pollution
     Control Federation, _41, 199-207 (1969).

49.  Home, W. R. and llurse, J. E. Proceedings of the Eighteenth Industrial
     Waste Conference (1963), 169-173, Purdue University.

50.  Ludberg, James E. and Nicks, G. Donald, Water and Sewage Works,
     IW/10-13, November 1969-

51.  Cousins, W. G. and Uindler, A. B., "Tertiary Treatment of Weak
     Ammonia Liquor from Coke I3y-Products Plant," presented at the Water
     Pollution Control Federation Meeting, Boston, Mass. (1970).

52.  Ashmore, A. G., Catchpole, J. R., and Cooper, R. L., Water Research,
     !_._, 605-624 (1967).

53.  Delxjiche, C. C. , Inorganic Nitrogen Metabolism, Johns Hopkins Press,
     Baltimore, Md. (1956).

54.  Fry, B. A., The Nitrogen Metabolism of Micro Organics, Methuen and
     Co., London (1955).

55.  Alexander, !Iartin, Introduction to Soil Microbiology, John Wiley
     and Sons, New York (1961).

56.  Ludzack, F. J. and Ettinger, M. B., "Controlling Operation to
     Minimize Activated Sludge Effluent Nitrogen", Paper presented to
     Water Pollution Control Federation, Milwaukee, Wisconsin, October
     (1961).
                                    108

-------
57.  Balakrishnan, S. and Eckenfelder, W. W.,  "Nitrogen Relationships in
     Biological Treatment Processes  - I.  Nitrification in  the Activated
     Sludge Process", Water Research, _3,  73-81 (1969).

58.  Balakrishnan, S. and Eckenfelder, W. W.,  "Nitrigen Relationships in
     Biological Treatment Processes  - III.   Denitrification in the Modified
     Activated Sludge Process",  Water Research.  3^,  177-188  (1969).
            V
59.  Barth, E. F., "Chemical-Biological  Control  of  Nitrogen and Phosphorus
     in Wastewater Effluent",  J. Water Pollution Control  Federation, 40,
     2040  (1968).              ———

60.  Downing, A. L., "Nitrification  in the  Activated Sludge Process",
     J. Institute of Sewage Purification, 2_,  130-158 (1964).

61.  Downing, A. L. and A. P.  Hopwood, "Some Observations on the Kinetics
     of Nitrifying Activated  Sludge  Plants",  Schweizerisch  Zeitschrift
     fur Hydrologie. 26, 1145-54 (1964).

62.  Finsen,  P. 0. and  D.  Sampson, "Denitrification of Sewage Effluents",
     The Water and Waste Treatment Journal  (England), May/June (1959).

63.  Denne, A., and R.  Gross,  "Industrial Experience with a Plant for
     the Biological Treatment of Phenol-Containing  Coke Oven Effluents",
     Stahl and Eisen,  88,  280, (March, 1968).

64.  Fisher,  C. W., R.  D.  Hepner, and G.  R. Tallon, "Coke Plant Effluent
     Treatment Investigations",  Presented at Easter States  Blast Furnace
     and Coke Oven Association Meeting,  Pittsburgh, Pennsylvania, (Feb.*
     1970).

65.  Gunderloy, Frank  C.,  Jr., Cliff Y.  Fujikawa, V. H. Dayan and S.
     Gird, Dilute  Solution Reactions of  the Nitrate Ion as  Appliedto
     Water Reclamation, U.  S.  Department of the Interior, Federal Water
     Pollution Control Administration,  Cincinnati,  Ohio.  October, 1968.
                                     109

-------
                           SECTION XIII
                           PUBLICATIONS
The work performed during the pilot study has been previously described
in the following publication.
   Barker, John E. and Thompson, Pvonald J.,
   "BIOLOGICAL OXIDATION OF COKE PLANT WASTE"
   Presented at Chicago Regional Technical
     Meeting of A.I.S.I., October  14, 1971
                                     111

-------
                            SECTION XIV

                             GLOSSARY


Aerobe - organisms which require molecular oxygen.
Anaerobe - organisms which live only in the absence of molecular oxygen
Autotroph - organisms that rely entirely on inorganic compounds for
            nutritional requirements.

BOD-5 - 5-day, 20 °C biochemical oxygen demand.

C     - substrate concentration in reactor.
CCOD  - COD concentration (mg/1) .
CD    - dilution water conductivity.
Ce    - estimated plant cost.
Cg    - effluent conductivity or substrate concentration.
Cj    - influent substrate concentration.
0^    - liquor conductivity.
Cn    - new plant cost.
      - nitrate concentration (mg/1).
      - nitrate concentration  (mg/1) .

cnwmin. - cubic centimeters per minute.
COD   - chemical oxygen demand.
Chemosynthetic - organisms which depend on oxidation-reduction reactions
                 of inorganic  substrates  for energy for growth.
Complete-mix - a system in which the influent is mixed immediately with
               the entire contents  of the vessel resulting in a mixture
               whose properties are uniform and identical with those
               of the effluent.

dia.  - diameter.
D_nn  - Stoichiometric COD dosage  (mg/1) .
e~    - electron
election acceptor -  that  material  that  is  reduced  in biological reactions,
                     In  aerobic  systems  it  is  oxygen; in the anaerobic
                     denitrification system it is nitrogen.
epl   - equivalents  per liter.

facultative - organisms which can  live  in  either the presence or absence
              of molecular  oxygen.
ft.   - foot.
F     - free energy

gal.  - gallons.
gpd   - gallons per  day.
gal/day /ft2 - gallons per day per  square foot.
                                     113

-------
heterotroph - organisms which utilize organic carbon for energy and growth,
hp    - horsepower.
hydrogen acceptor - the oxidizing agent in biological reactions.
hydrogen donor - the oxidized substrate in biological reactions.

kcal  - kilocalories.
kg/cal/mole - kilogram-calories per mole.
K     - proportionality constant.
Km    - modified constant.

lime-distilled - excess ammonia liquor which has been stripped of fixed
                 ammonia by increasing the pH to about 11.0 with lime
                 and passing it through a still.

meq/1 - milliequivalents per liter.
mgd   - million gallons per day.
mg/1  - milligrams per liter.
ml/min. - milliliters per minute.

OC    - organic carbon.

ppb   - parts per billion.
ppm   - parts per million.

Q     - volumetric flow in the system.
Q     - quantity of dilution water.
Q     - quantity of liquor.
 Lt                 :' •
r     - ratio of new to assumed waste volume.
redox - oxidation-reduction potential.

S     - viable organism concentration in reactor.
Seechi disk - a target plate mounted on a calibrated rod which is used
              to determine the relative turbidity of water.
sludge bulking - the condition where the solid mass floats in the final
                 clarifier of a biological treatment plant.  This
                 condition is frequently caused by the denitrification
                 and the formation of nitrogen gas in the sludge solids.
spent pickle liquor - waste acid which is nearly saturated with iron
                      from acid cleaning or pickling steel.
SWD   - side wall depth.

T     - residence time in reactor
T     - total required COD (mg/1).
 Ov/ls
TPM   - tons per month.
        2
UMHOS/CM  - micro-ohms per square centimeter.

V     - volume of reactor.

X     - scaling factor.
                                  114

-------
                 SECTION XV
                 APPENDIXES
A-l  Analytical Data for Excess Aramoniacal
     Liquor

A-2  Analytical Data for Effluent from the
     Carbonaeious Unit

A-3  Analytical Data for Effluent from the
     Nitrification Unit

A^4  Analytical Data for Effluent from the
     Denitrification Unit

B-l  Analytical and Operational Data for the
     Carbonaceous Unit

B-2  Analytical and Operational Data for the
     Nitrification Unit

B-3  Analytical and Operational Data for the
     Denitrification Unit

C   Alkalinity Balance  for Nitrification
                          115

-------
APPENDIX A-l:  BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS  FROM COKE PLANT WASTES
                      ANALYTICAL DATA FOR EXCESS AMMONIACAL LIQUOR


DATE




2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
8
9
10


1
B
I*
j§
H

64
53
52
67
65
62
67
62
55
63
65
67
72
73
60
59
68
72
61
68
61
66
65
65
60
62
64
69
69

74
66
66
61
64
64
70
66
57
58
60
61
70
65
63
77

60
60
62
67
69
65
64
72
63
63
69
69
59
68
66
69
66
68
75
73
71




3.


8.6
8.6
8.6
8.5
8.2
8.8
8.8
8.6
8.8
8.9
8.6
8.6
8.7
9.0
9.0
9.0
9.0
8.9
8.9
8.7
8.7
8.7
8.9
8.8
8.8
8.7
8.6
8.6
8.6
8.8

8.8
8.9
8.9
8.9
8.7
8.6
8.7
8.6
8.7
8.8
8.6
8.7
8.5
8.5
8.4
8.4
8.3
8.8
8.7
8.6
8.9
8.8
8.9
8.3
8.9
9.2
9.0
8.8
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8.7
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-------
APPENDIX A-I:  page 2 of 6




DATE



4-11-70
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
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2
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6
7
8
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10
11
12'
13
14
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16
17
18




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79
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77
80
76
81
74
79
78
69
70
75
78

90

84
78
80
88
88
71
80
81
78

88
79
88
78
101
84
87
82
85
83
85
85
87
83
77

87





*




8.6
8.4
8.5
8.6
8.5
8.4
8.5
8.3
8.5
8.3
8.6
8.4
8.4
8.6
8.5
8.2
8.2
8.5
8.4
8.4
8.4
8.5
8.5
8.4
8.7
8.5
8.8
8.5
8.5
8.6
8.6
8.7
8.5
8.5
8.6
8.6
8.5
8.6
8.5
8.6
8.2
8.5
8.4
8.8
8.7
8.6
8.7
8.6
8.5

8.7
8.6
d.6
8.6
8.7
8.7
8.7
8.6
8.6
8.5
8.5
8.5
8.6
8.6
8.7
8.5
8.6




» o"
E 5
if
1 »



1700
1500
2000
1700
1490
1500
1640
2700
1320
1220
1850
1340
1490
1900
1440
1070
1020
1520
1200
1300
1425
1400
1500
1360
2200
2000
1750
1425
1250
890
1860
1800
1650
1380
1750
1750
1590
1960
1740
1900
1400
1500
1250
: 2350
2040
2040
2000
1740
1500

2200
2000
1900
1900
2200
2125
1880
1690
1810
1720
1530
1480
1550
1400
1670
1240
1450


„
9
i ;
a »
It
-


2880

3947

2327


3440

2842

2470


1990

1918

1550


966

1619

1720


1580

1500

1515


2380

822

791


1060

1209

928


1370

1200

2980


1020

713

1414


1400

675

OXYGEN
DEMAND,
ng/1 02


3
i
























3400



























4140















3620

3
|l
U tf"l
M
0)























1710



























2370






















M to
i
9S (-1
If



730






1130






846






556






665






850






634






760






700






906








in "
Bf



13

35

18


17

26

17


21

24

34


23

30

31


33

35

34


11

37

37


35

35

24


34

42

41


24

27

40


20

27





1
11
If



240






394






548






400






366






230






98






356






410






360








8"
it



2






2






0






2






3






2

4




6






4






0






0



NITROGENOUS
COMPONENTS ,
mg/1 N


g
i



1760

3810

3230


3330

4240

4100


3500

3740

3190


3210

3490

3330


3370

3640

3610


3250

3540

3420


3150

3080

3120


3150

3300

3570


3420

3860

3770


3930

3720


y S
§i










253






199






116






196






193






224






230






14






375




i
i







































































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g










































































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1?
if




















































70





















„
§ -.
H 0
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44
















































E e
!«

§ u
8-g



12000

24300

21600


24600

27000

25800


23400

23900

20580


21800

20900

19400


21400

24300

22400


19500

21900

20800


21200

18000

19700


26000

20000

20800


21300

23800

22400


25500

29600

                                          118

-------
APPENDIX A-li  page 3 of 6


DATE



6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-80
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26


1
3*
S
1
92
86
84
83

90
87
94
91
88
89
89
89
93
88
96
85
85
89
87
94
93
87
88
84
87
88
88
88
88
88
86
88
85
81
91
98
88
88

90

92
87
89
85
93
90
88
88
91
102
90
95
98
88
86
99
88
108
90
106
91
92
86
96
108
90
83



OB
0.

8.5
8.7
8.6
8.5
8.6
8.7
8.6
8.6
8.7
8.5
8.3
8.4
8.4
8.3
8.5
8.4
8.5
8.3
8.2
8.2
8.4
8.5
8.4
8.4
8.4
8.4
8.4
8.3
8.4
8.4
8.3
8.3
8.3
8.4
8.6
8,3
8.6
8.5
8.4
8.4
8.3

8.4
8.4
8.5
8.4
8.6
8.5
8.6
8.4
8.6
8.5
8.5
8.4
8.5
8.5
8.5
8.6
8.6
8.7
8.6
8.6
8.7
8.6
8.6
8.7
8.6
8.5
8.9


S cf
3 u
2 "M
sj
1300
1790
1400
1400
1500
1680
1800
1680
1950
1680
1300
1300
1330
1180
1380
1250
1425
1380
1200
11OO
17OO
1440
1200
1500
1280
1450
1490
1200
1150
1350
1100
1200
1150
1135
1450
960
1550
1515
1640
1550
1220

1600
1400
1510
1350
1600
1400
1750
1290
1420
1650
137O
1130
1720
1400
1550
1650
1480
1580
1150
1580
2150
1600
1390
1610
1560
1925
1880

i
u
a °
BE -i
< --
U &G

272

578

586

272


521

602

834

























950




1620














880



OXYGEN
ng/1 02

|
£
g
1770

3380

3650

3340


3390

3440

3190


3440

3370

2990


3160

2920

2880


2910

2700

2960




3140

1310


2920

2580

2729


2790

2740

2970

3079
2910
2860

4010
2360
3
£ «
9 i
w
CO
















1830
















































«t
sf
55 1-1
idt


650






650






580






485






540













420






500





550



706




SB
H°

Sff
19

24

31

28


17

30

25


29

19

34


28

31

22


24

24

27




24

27


27

21

23


25

21

33

26
26
17

19
28


ts
Is
>* (A
O r* •
15f


290






370






350






304






314













300






324





290



426




sV
E-,
5 bo
w S












































2












4



2

NITROGENOUS
COMPONENTS ,
mg/1 N

2
§
i
3820

4100

4470

3710


3650

3710

3720


3440

3500

3560


3790

3670

3630


3280

3280

3260




3400

3200


2720

2770

2650


2730

2700

3230

2580
2690
2530

3900
1690

H 0
1 i
o z


179






179






182






154






258













104






106





120



143


1
K
Z
































































H
es
H
H


































































„
Ed
1?
« "-<
P "5
CU Q
















61



























50





















g-
M O
O *~>
&~&
o S

































































SJ5
*•« O
B £
§1
29000

29600

32100

24800


18000

25600

26500


25200

23900

26000
•

28700

28100

27300


24000

23100

26300




23500

23800


20700

20000

18900


20000

19800

22300

17800
18000
18400

27500
10000
                                        119

-------
APPENDIX A-l!  page 4 of 6



DATE


8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
10-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
16
19
20
21
22
23
24
25
26
27
28'
29
30
31
11-1-70
2
3



If

s
78
85
83
84
88
79
83
84
87
85
89
86
87
90
85
84
84
84
91
87
81
87
85
84
87
84
90

81
84
80
75
72
70
79
75
85
81
79
82
94
83
87
64
70
71
72
70
68
69
67
67
65
65
65
67
73
76
70
72
76
80
76
64
66
65
67
64
62



SB
b

8.2
8.8
8.7
8.6
8,6
8.5
8.6
8.6
8.6
8.6
8.9
8.6
8.5
8.5
8.5
8.6
8.7
8.6
8.5
8.6
8.5
8.6
8.6
8.6
8.6
8.5
8.6
1
8.8
8.5
8.4
8.6
8.7
8.7
8.5
8.6
8.7
8.7
8.6
8.6
8.6
8.4
8.5
8.5
8.7
8.7
8.7
8.7
8.7
8.6
8.6
8.6
8.7
8.8
8.9
8.8
8.7
8.7
8.7
8.7
8.6
8.6
8.7
8.6
8.5
8.6
8.6
8.6
8.8



if
9 C

1540
2100
1850
1270
1950
1250
2045
1230
2080
2100
1720
1700
1950
1920
2150
2160
2580
2640
1900
2700
1970
2340
2300
2250
2300
2020
2400

2340
2350
2230
2280
2280
2260
2250
1920
3050
3025
2650
2760
2600
2640
2450
2120
2500
2480
2450
2260
2270
2275
2000
2000
2010
2300
2500
2600
2315
1975
2130
2140
1850
1800
1800
1660
1660
1850
1820
1660
975


i
8 °
5 ^
i &





































































OXYGEN
DEMAND,
ng/1 02
g
3B
1

2010


5680

7700

7390



7910
9664

9530


8500

9040

8610


9390

8200

9490


9680

9550

10900


10600

10100

9790


8910

10200

9230




6960

8450


9142

6170

5320


4773

||
SS i
B


















6170




















5790



























2460




.8
P
9S i"^
If




1240







1700


1980


1740






1900






2150






2380






652










8.0


1900






915




*
!8
M *"^
Bf

24


14.1

17

12



8.7
13

15


15

12

20


24

15

26


13

20

21


25

23

14


21

11

8




25




12

28

20


26




1
O **4
iff




440







530





768






1540






628






1100






660













480






540




ft
5 w
W f^
8 ff




2







1





1






1






2






2






4




















3

NITROGENOUS
COMPONENTS ,
ng/1 »
a
O
1

1690


3230

3040

2930



3120
3920

4200


4410

4200

4000


4160

3370

3320


3370

3780

4170


4120

4000

3950


3930

3750

3800




4100

4370


4130

3670

3780


3440

O w
•S ffi
1 z




137







146





230






196






165






188






260













230






204

1

H
Z





































































R
p6
S







































































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Ik
o ^^
E ff


















49




















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34




A
u
S3
O ivl
3 **
iff





_































































-

>* ••
Ek
t
S o
§1

12100


22800

22000

20700



21800
26900

28600


30100

28700

28600


28200

23000

20800


23200

23800

26800


28800

27100

28100


28800

27100

27800




28600

29900


29600

26500

27200


25100

                                         120

-------
APPENDIX A-l:  page 5 of 6



DATE


11-4-70
5
6
7
8
9
10
11
12



u
1
S--
*
62
59
66
67
77
73
66
67
68




EX

8.8
8.8
8.7
8.6



• Cl
£ 8
i *
s f
1880
2000
2000
1850
8.5 1800
8.5
8.5
8.4
8.5
13 67 8.7
1650
1680
1470
1800
2100
14 60 8.7 i 1570
15 j 60 8.8 2100
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
52
68
71
68
72
65
70
60
49
86
67
75
74
74
72
73
80

73
74.
71
65
70
71
68
70
57
58
57
64
67
70
71
70
71
73
74
66
66
54
54
68
70
68
60
58
62
70
57
50
50
44
42
50
63
65
8.9
S.8
8.7
8.7
8.6
8.6
8.6
8.6
8.5
8.7
8.5
8.4
8.3
8.1
8.5
8.5
8.5
8.6
8.4
8.4
8.4
8.5
8.5
8.8
8,9
8.8
8.7
8.6
8.6
8.8
8.9
8.3
8.5
8.5
8.6
8.6
8.4
8.6
8.5
8.6
8.5
8.6
8.6
8.7
8.7
8.6
8.7
8.7
8.7
8.6
8.7
8.6
8.5
8.8
8.8
8.7


Z
1
a °
is
t3 00
o












2060
2130
2180
2125
1900
1900
1700
1725
1650
2100
1490
1300
1250
1060
18^0
1750
1725
1650
1320
1575
1520
1320
1325
2650
2550
2300
2280
2100
2130
2550
2400
1900
2180
1600
1950
1800
1600
1900
1930
1650
1560
2450
2180
2560
2425
2170
1920
2270
2020
1950
1980
2050
1800
2500
2425
2220











































„ .

OXYGEN
DEMAND,
mg/1 02

a
V
4920

15600


5465

5210

5930


6160

4620

5450


5471

5870

5570


5915

6143

6040


13800

6930

7220


5900

5960
5520

5650
6560
6400

6700
6450
6580

7210
6170
5920

5390
3
J!
a

































4160



















4030







«l
1!
-f





1070






1080






1110






1120






1480






1180




1100



1290



1310



1010




|-
Bf
26

52


26

17

12


30

23

18


14

30

11


20

21

13


21

35

30


31

34
24

20
22
25

23
20
14

18
12
27

28



1
i!
?»





640






540






560



11


690






692






652




640



648



668



612




1:
£1?





2






3






<1






0.4






1






4




1



4



1



2
NITROGENOUS
COMPONENTS ,
mg/1 N

a
*
3890

4400


3930

4140

3700


3420

3822

3470


3530

4120

3540


3900

3750

3720


3960

4720

3720


4120

4420
4260

4200
2560
2510

2410
2030
1960

2060
1974
2000

2130

li
ii





204






90






140






168






255






176




252



700



2300



2100

13
*



























































E
g
M





























































-
If
It

































60



















52








§3
of




























































N* C
3-1
> a
II
O -H
u e
27200

31700


28600

30800

26600


24900

26900

24800


27300

28700

27100


28650

27200

28200


27500

33100

28200


28300

31400
32200

31700
30600
28200

28900
30300
28700

30100
31100
32900

29600
                                         121

-------
APPENDIX A-l:  page 6 of 6



DATE

1-12-71
13
.14
15
16
17
18




lEHPERATURE
•F

80
82
78
75
62
65
66




X
&

8.7
8.6
8.6
8.6
8.7
8.7
8.7




* C"1
£ 8
H «
S °
3 <
I *

2700
2700
2450
2050
2450
2460
2210



'g
S °
§ <
S f









OXYGEN
DEMAND,
mg/1 02
CHEMICAL


5790

5763


5940

IOCHEMICAI
5- day
m











PHENOLICS ,
mg/1 C6H50H







1200




U ^
s°
11


21

21


32




THIOCYANATE
mg/1 SCN







648




SDIFIDE,
mg/1 S







2

NITROGENOUS
COMPONENTS ,
mg/1 N
|


3950

3976


4450

ORGANIC
NITROGEN







84
i
NITRATE









NITRITE












PHOSPHATE,
mg/1 P04








•



CHLORIDE,
mg/1 Cl











>4 E
CONDUCTIVIT
micromhos /c


28800

29600


29700

                                        122

-------
APPENDIX A-2:  BIOLOGICAL REMOVAL OF CARBON AMD NITROGEN COMPOUNDS FROM COKE PLANT WASTES
                ANALYTICAL DATA FOR EFFLUENT FROM THE CARBONACEOUS UNIT

DATE

2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
U
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
8
9
10

i
i


























































8.3
8.3
8.5
8.3
8.3
8.4
8.4
8.4
8.3
8.3
6.5
8.4
8.2
8.1
8.3
8.4
6.5
8.4
8.1
8.2
8.0
8.2
8.1
7.8
8.3
8.2
8.3
8.3
8.3
8.3

8.4
8.1
8.0
7.7
8.3
7.5
6.8
7.5
6.4
6.5
6.9
6.7
6.4
6.3
6.4
6.5
6.4
8.0
8.0
6.9
6.9
6.9
6.9
6.6
7.5
7.5
7.0
7.2
6.7
7.2
6.8
7.0
8,4
8.5
8.3
8.2
8.5
8.5

e 
-------
APPENDIX A-2:  page 2 of 6



DATE



4-11-70
12-
13-
14
15
16
17
18
19
' 20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18



|
1*
§









































































x




8.5
8.5
8.2
8.3
8.3
8.1
8.2
8.0
8.1
8.0
8.1
8.1
8.2
8.2
8.2
8.0
8.0
8.0
7.7
7.8
7.0
7.8
7.9
7.8
8.2
8.2
8.5
8.3
8.2
8.3
8.2
8.3
8.2
8.3
8.2
8.2
8.2
8.2
8.3
8.2
8.2
8.2
8.0
8.3
8.3
8.4
8.3
8.3
8.2

8.3
8.0
8.4
8.4
8.2
8.2
8.3
8.3
8.3
8.3
8.3
8.3
8.5
8.3
8.4
8.1
8.3



K cf
w A
25 U
4 f



500
425
320
375
350
380
360
310
375
335
400
390
420
350
455
400
270
270
240
240
125
275
325
335
600
685
60O
600
450
590
525
550
550
600
600
500
625
725
590
650
600
525
440
700
625
750
675
650
625

790
525
990
920
860
950
975
1360
1020
1070
1010
990
980
450
940
620
700


g
u
0 0
[2 !— 1
0 ^



74

22

44


83

104

66


71

92

66


52

61

150


45

60

64


102

247

62


52

1209

33


148

90

287


92

59

166


613

39
OXYGEN
DEMAND,
mg/1 02

i
o




































































1700
3
ii
H *°
«
























i














































wt
s «^.
53 tip



0.2






0.1






0.2






1.0






0.1






0.2






0.2






5.0






0.57






0.60






ss
H
Bff



1.5

0.9

1.5


20

6.2

4.9


3.7

2.8

2.7


3.3

3.9

5.8


4.3

11

4.6


4.7

5.1

10


5.4

35

5.4


5.1

10

6.2


6.0

6.2

5.5


6.2

9.1



i
35
b* tn
g-*^
%



64






79






113






22






164






86






198






180






620






340






I:
VI 6
























0.2












































NITROGENOUS
COMPONENTS ,
ng/1 N

g
|



399

252

599


788

1120

1220


1360

1150

1190


1170

1400

1700


1510

1640

1640


1690

2020

1970


1652

3080

1760


1720

2100

2440


2560

2860

3040


2940

2860

ll
g g



43






45






59






59






76






87






200






161






196






200



1
H
X



1.0

0.8

1.1


3.7

6.3

6.3


2.9

6.6

5.4


7.3

6.9

5.1


5.9

4.6

2.3


1.5

1.5

0.7


1.0



0.5


0.5

0.1

0.1


0.3

0.2

0.2


0.5

0.3

1
g








































































B"*
1?
M 00
^ 3








































































„
3^
if







































































>« 6
P 5
B^
H|
5S W
O S



4000

3510

5680


7480

9820

9860


10780

9560

9390


9730

11000

12500

,
12600

14000

12200


13300

15000

14700


14100

18000

13200


14900

14600

16600


17400

19400

20300


21700

23500
                                         124

-------
APPENDIX A-2:  page 3 of 6

DATS


6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
. 15
16
17
18
19
20
21
22
23
24
-1 25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26

1
•f
1
































































X
a

8.1
8.3
8.3
8.1
8.2
8.2
8.2
8.1
8.2
8.1
8.0
8.1
8.0
8.0
8.0
8.0
8.0
7.8
8.0
7.9
8.0
8.0
8.0
8.1
8.0
8.0
8.0
8.0
7.8
8.0
8.0
7.9
8.0
8.0
8.3
8.0
8.1
8.1

7.9
7.7
7.9
7.9
8.0
8.0
7.9
8.2
8.0
8.2
8.0
8.2
8.1
8.1
8.0
8.2
8.2
8.2
8.2
8.1
8.1
8.2
8.2
8.6
8.2
8.1
8.1
8.2
8.2
8.0

BiT
M «
55 O
!* f
360
525
475
375
525
365
640
475
475
415
380
325
325
325
350
425
430
280
500
520
375
350
355
400
325
380
340
400
185
350
350
310
400
380
550
420
480
540

430
235
400
415
525
550
415
640
390
660
435
550
475
510
460
450,
620
565
515
540
455
530
475
720
470
525
445
535
550
485
.
1
O O
W
ii
Otf E*
24

51
43
22


18

33

53

























41




















72



OXYGEN
DEMAND,
mg/1 02

i
u
1030

875
955
1000


667

719

645


716

727

725


803

532

512


546

793

867




1140

816


788

696

725

665


695

707


777
774
1190

895
903
3
g "O
M































































-g
CO u*1
U S
§*
11


0.34




0.2






0.2






0.2






0.2













0.3





0.2







0.17



.30



bl Z
S"
si
6

4.2
4.4
5


4

6.7

9.1


11

5.6

4.7


3.5

3.7

3.1


3.5

4.3

5.0




5.0

6.3


5.5

5.0

4.3

4.7


6.1

8.5


4.9
4.5
4.6

6.0
5.7

IS
ft* CO
t-t *""«
Ef


240




154






164






174






174













190





250







220



274



8«
B-
If




























































0.6

NITROGENOUS
COMPONENTS ,
mg/1 N

I
1
1810

1820
2180
2320


1740

1790

1840


1880

1920

1760


1580

1670

1270


1620

1760

2240




1920

2160


2220

1880

1820

1740


1780

1850


1940
1700
1670

1710
2240

55
as
5S
O H
S £


98




102






42






88






143













119





80







92



84


1
H
^ H
SE
-

0.2
0.2
0.4


0.2

0.1

0.3


0.4

0.3

0.4


0.3

0.2

0.4


0.7

0.3

0.3




0.3

0.4


0.4

0.3

0.6

1.1


1.0

0.5


0.8
0.5
1.4

0.5
0.3

S
S
a































































K
EC
\€
EO »-i
11
































































g-
g-
o































































1^
M O
i!
§0
•rt
U S
15600

15100
18100
17800


15100

15600

15800


15400

15300

14400


13800

14900

11200


14100

14400

19700




16400

18000


18800

16500

15100

14300


14400

14700


15900
13800
14400

14700
18400
                                         125

-------
APPENDIX A-2:  page 4 of 6



DATE


8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
; 23
24
25
26
27
28
29
30
10-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
11-1-70
2
3



i*
i















X


7.7
8.0
8.2
8.0
8.1
8.1
8.1
8.0
7.9



E C
a ^
1 ~*

500
575
650
335
415
500
575
575
490
8.0 550
7.9
; 7-S























































7.8
7.8
7.8
7.8
8.0
7.9
7.8
8.0
7.8
7.9
7.7
7.9
7.9
7.8
7.9

8.0
7.9
7,9
7.9
7.8
8.2
7.8
7.9
18.1
8.0
8.0
7.9
8.1
7.8
7.9
7.8
8.0
8.1
8.0
8.1
8.1
8.0
8.0
8.1
8.0
8.1
8.2
8.1
8.1
7.9
8.0
8.0
8.0
8.0
8.0
8.0
8.0
8.0
8.2
8.2
8.3
475
300
410
340
550
475
660
560
465
675
590
670
540
625
575
475
650

640
550
575
625
575
825
475
645
980
955
900
725
725
560
550
380
475
450
420
420
380
350
325
375
400
295
340
375
350
330
365
375
360
345
400
425
480
525
540
370
525


z
u u
2 *"*
i ^

































,


































OXYGEN
DEMAND,
ing /I 02

i
i


900


693

785

2960



1250
1319

1850


2060

2440

2390


2380

2240

2020


1993






2740

2330

1550


766

629

583




602

567


732

807

895

592
1*
g*>
ta



























































i










.8
as
jS £0





.22







0.2


0.90
i

1.1






1.2






11






16






0.2













0.2





0.2



*!
1^


4.6


2.7

3.3

4.1



4.3
5.0

4.6


4.6

2.4

5.4


5.8

8.4

5.9


5.9






5.6

5.0

3.4


1.7

2.0

1.2




1.6

1.8


2.9

2.8

8.5

3.0



IB
ll





144







270

,
'


394






1220






394






628






150













220





190



1:
B u
w s




































































NITROGENOUS
COMPONENTS ,
mg/l N

|
|


1870


1040

1530

1920



1730
1890

2480


2600

2860

2630


2520

2480

2160


238






2340

2020

1350


686

520

504




658

700


931

1140

1510

1080
•1
1 i





98







115





176






153






77






80






99













74





62
1
H
Z


0.6


0.8

0.4

0.1



0.3
0.2

0.1


0.3

0.6

0.1


<0.1

0.3

0.2


0.3

•




0.5

0.3

0.4


0.2

0.3

0.3




0.4

0.5


0.3

0.2

0.4

0.1
B
i













































•'<

























Ik
§ i







































































a"-
M CJ
s c
fi3
u IP







































































IDUCTIWITY
iromhos/cm
ft w
81


15200


9630

14000

15800



14600
16300

20600


21400

23200

22400


21500

20000

17600


17000






19800

16800

12500


6240

5100

5040




6010

6600


8700

11500

12900

9740
                                          126

-------
APPENDIX A-2:  page 5 of 6



BATE
^\
11-4-70
5
6
7
.. 8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
.,12-1-70
2
3
4
5
6
7
8
9
10
II
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-70
2
3
4
5
6
7
• 8
9
10
11
nm^mmmmmiiiifm


!r




























































mttffftft^fmfrmm


X
o.
8.3
8.4
8.2
8.2
8.1
8.0
8.0
8.0
8.1
8.2
8.3
8.3
8.4
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.0
8.0
8.0
8.1
8.1
8.1
8.2
8.0
8.1
8.1
8.0
8.0
8.2
8.4
8.3
8.2
8.1
8.1
8.3
8.3

8.3
8.1
8.2
8.1
8.1
8.0
8.0
8.0
8.1
8.1
8.1
8.2
8.2
8.2
8.5
8.3
8.2
8.3
8.3
8.2
8.2
8.0
8.2
8.2
8.1
**M>*qBBM^


ALKALINITY,
mg/1 CaCO,
560
570
725
690
650
575
595
580
625
625
660
750
825
1625
575
520
425
400
400
400
380
390
380
325
300
, 280
320
350
340
350
320
400
350
280
300
490
600
650
570
525
510
600
525

5OO
500
520
440
510
450
410
460
460
580
625
650
660
625
510
645
600
580
550
450
325
35O
575
415
424


§
s °
3 <
1 »




























































«»MM«MM^.wn_
OXYGEN
DEMAND,
rag /I 02
CHEMICAL
672
1680

928
1030
1080


1280,

697

658


582

419

344


445

417

516


538

517

782


840

729

688


698

692

660


757

654

594
646
727
767

764
CHEMICAL
5-day
o
M
ra































































-g
i3£
H iO
Si °
!~i



0.6




4.3






0.4






0.1






0.1






0.2






0.1






0.3




0.2



6.3
-


tans
8°
S~
Ss^J
o 3
3.1
6.4

5.0
5.5
12


12

3:8

2.4


2.7

2.6

2.2


2.9

4.9

4.0


3.3

4.8

7.4


5.0

6.4

6.3


6.1

e.i

4.7


5.6

5.01

4.3
4.4
5.0
4.8

5.4
H.l^^^»»


si z
fis
O P-4
gff



290




306






140






180






250






280






280






284




284



294



S»
V,.,
^ bfl
M S
















-------
APPENDIX A-2:   page 6 of 6



DATE




1-12-70
13
14
15
16
17
18
19
20



i
I*
Mo
i















'X
&

8.2
8.1
8.2
8.1
8.2
8.3
8.2

•



B 8"
SB! O
h>) •-<
i *

450
525
615
540
625
575
525




i
1
t) O
Z tH
1 *










OXYGEN
DEMAND,
ng/1 02

2
H
1


754

659


689

674
d
I i«
g] "O
r
ca


'





'



A
B *
o
if







0.2






SS
RP
Iff


5.7

5.4


4.7

3.8



1
|s
u
Iff







284






B w
W
ll










NITROGENOUS
COMPONENTS ,
mg/1 N

g
SB
•|


1690

1680
/

1670

1250

g 1
5 s
II







70



s
5
g


0.6

0.8


0.8

1.2

S
•M
g



'









B .»
i ^
W KM
1 f













A
i G
?3 •-!
M ***












A
&•» B
64
M O

& B
z u
O •H
u e


14200

14000


13500

11700
                                         128

-------
APPENDIX A-3:  BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES




                 ANALYTICAL DATA FOR EFFLUENT FROM THE NITRIFICATION UNIT


DATE

2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
g
9
10
_ _ 	 i


1
I'


















































1










'£
6.5
6.6
6.7
7.5
6.4
6.4
6.4
6.9
6.7
7.0
6.9
7.0
6.6
7.2
7.2
6.5
8.5
6.8
6.3
6.4
6.4
6.6
6.5
6.3
6.3
6.3
6.2
6.2
6.4
6.4
6.3
6.4
6.2
6.7
6,7
6.7
6.2
6.4
6.0
6.4
6.5
6.5
6.3
6.1
6.0
6.3
6.3
6.5
6.5
7.0
6.5
6.7
6.5
6.3
6.4
6.3
6.2
6.2
6.0
6.4
6.5
6.5
7.1
8.3
6.6
6.3
6.3
6.4


• M
4 O
ALKALINI:
ng/1 Cai
136
85
86
95
174
47
48
91
79
71
95
95
869
118
162
126
443
105
80
70
100
100
90
90
90
110
75
45
45
50
45
65
60
75
50
50
60
40
55
40
100
50
45
35
60
55
45
120
55
75
105
70
75
50
45
125
55
55
70
68
90
60
75
225
40
30
30
55

§
i
s °
5 *H
1 f

54

35

37


39

36

36


39

36

27

27
21
23

21
17
16

19
18
10

16
13

16


18

13

23


16

23

39


27

16

15
OXYGEN
DEMAND,
rag /I 02

1 CHEMICAL

























































HXM-^B^—^-
d
if
r




























































-8
£A l*n
3 ae
i "
If

























































- 	 —



CYANIDE,
ingA CN

























































	


s
is
K
Bff






























10
9

10























i ^ ii "



g"M
E-
If




















































•





NITROGENOUS
COMPONENTS ,
ng/l N

|

213

186

160


200

237

225


161

160

200

164
141
178

167
132
81

97
136
151

178
206
147


241

221

197


216

310

302


144

62

29
	

, ORGANIC
NITROGEN



























































NITRATE
.
47

33

47


56

52

51


71

70

74

68
70
70

70
80
97

90
93
84

87
87
95


102

96

126


87

96

131


122

96

135


NITRITE

48

34

39


48

48

50


55

59

59

51
63
64

56
67
75

91
94
76

69
64
73


63

75

90


110

107

147


128

95

116



Dd
PHOSPHAT
mg/1 ?04




























































*
CHLORIDE
ng/1 Cl






























486
486

523

























P* fi
•4  0)
55
II
Si

2920

2790

2620


2860

3100

2990


2390

2420

2500

2280
2570
2810

2890
2580
2100

2630
2840
2820

2840
3250
2790


3030

3110

3250


3520



4230


3860

2500

2520

                                            129

-------
APPENDIX A- 3:   page 2 of 6



DATE
4-11-70
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18



TEMPERATURE
°F







































































£


6.8
6.4
6.2
6.7
6.5
6.4
6.7
6.5
6.9
5.8
6.7
6.7
6.7
6.9
6.6
8.0
7.9
7.5
6.8
6.8
7.7
6.8
6.8
9.0
8.6
8.3
8.4
8.0
7.6
6.4
6.2
8.2
8.3
7.8
7.5
7.5
7.5
6.6
6.3
6.7
6.4
6.4
6.7
7.2
7.5
7.5
7.8
8.0
8.0

7.9
7.9
8.2
8.0
8.0
8.0
7.0
8.0
8.0
7.3
6.7
6.3
6.6
7.0
6.1
6.7
6.4



ALKALINITY,
mg/1 CaCOj


500
40
35
50
45
50
45
40
60
60
75
65
70
75
65
:380
185
135
70
75
240
80
105
1120
715
500
450
300
120
15
35
300
400
215
160
180
145
40
40
25
20
20
25
135
100
140
220
370
360

175
140
250
245
(240
240
205
180
145
75
20
25
20
75
20
25
25


^
o o
M
§ <
g f
O


55

28

16


48

74

86


74

88

49

27


41

142


30

9

48


109

48

4


4

24

26


29

22

27

39

44

73


73

39

OXYGEN
DEMAND,
mg/1 02

CHEMICAL



































































"
£J *O
H
ea







































































M "")
0 EC
M %D
At







































































gg
M
Si







































































* .'»'
Bl







































































e-
M B




































































NITROGENOUS
COMPONENTS ,
mg/1 N

AMMONIA


136

223

193


416

728

994


609'

840

644

553


777

1360


567

259

1140


1620

875

364


182

749'

1430


1740

567

343

154

112

106


8

36

ORGANIe
NITROGEN




































































NITRATE


160

83

103


192

224

130


115

,296

400

441


366

61


34

66

45

,
21

50

63


54
w
131

103


,4.3

0.6

0.5

4.8

10

17


66'

108

NITRITE
i


182

122

230


254

220
i
172


185 '

283. '->

405

369


314 •"•
.
70


34

52

53


47

63

66


106

135

96


7.4

1.2

0.51

3.4

4.8

3.9


! 91

105 .




PHOSPHATE,
mg/1 P04







































































CHLORIDE,
mg/1 Cl






















































:'
















CONDUCTIVITY
mlcromhos /cm


4230

4040

5400


7750

10300

10300


10780

11300

11300

12800


11400

12200


5940

3530

11000


13000

8400

4310


3370

8150

12900


15600

4640

3310

1800

1940

1910


2060

2540

                                        130

-------
APPENDIX A-3:  page  3 of 6




DATE

6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26




1'
H































































X
ca.

8.0
6.7
6.8
6.5
6.4
6.8
6.8
6.4
6.4
6.6
7.0
8.1
7.6
9.9
8.3
7.5
6.4
6.5
6.5
6.6
6.9
6.9
6.8
6.8
6.8
6.7
6.7
6.7
6.8
7.7
6.7
6.7
6.6
6.7
7.2
8.0
8.0
7.8

7.7
7.7
8.0
7.9
8.0
7.8
7.4
6.7
6.6
6.4
6.8
6,7
6.6
6.6
6.5
6.5
6.2
6.6
6.6
6.6
6.5
6.6
6.4
6.4
8.8
8.5
8.4
8.4
8.3
8.1




I »

105
40
35
25
25
70
50
40
40
60
75
125
190
400
210
100
25
25
25
35
50
50
40
35
35
30
50
50
40
130
30
30
65
55
80
220
275
245

230
135
2OO
145
160
120
85
35
25
25
25
60
20
20
60
60
50
55
45
20
2.0
15
55
20
345
255
210
205
220
185



1
U
g »
o
24

17
43

6

7

18

21

























32






31










25


1
OXYGEN
DEMAND,

tug /I 02
a
°


219


213

277

404)

227


89

318

343


309

373

380


295

381

426




555

140


58

81

94


85
74
82

66
90
171

142
178
OCHEHICAL
5- day
g































































il
5 9































































*.
3 OB
o 9































































Is
8 tf































































u
g:
eft C?
























































!



NITROGENOUS
COMPONENTS ,
mg/1 N
i
1
136

100
134

61

69

27

197


228

262

232


214

239

277


361

339

899




1090

378


123

104

104


137
126
48

73
82
161

207
326
il
8 &



























































1
g
111

183
142

174

200

223

173


60

161

109


102

124

124


147

142

77

1


32

4.9


43

29

38


35
38
25

41
45
40

4.8
11
1
5
140

154
174

186

199

298

203


63 .
i
142
,
149


135

162
.
158


115

131

88




4.2

3.2


25

47

51


47
47
41

41
43
32

6.9
15




t? e?
GO i-*
Bi tf































































Is
£c oo
5 s






























































k. . ea
>in»cTivm
Lcrotnhos/cn
u e
4020

3890
4470

3840

4690

5680

4480




5180

4820


4730

5550

5610


5620

5830

10200




1020

4040


2170

2080

2030


2260
2240
1430 '

1690
1740
2640

2680
3850
                                       131

-------
APPENDIX A-3:   page 4 of  6



DATE


8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
10-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
11-1-70
2
3



W
i?
1°









































































X
o.
7.7
7.8
7.5
6.7
6.7
6.8
6.4
6.6
6.9
6.8
6.5
8.3
6.9
6.6
6.8
6.9
7.1
7.1
7.2
7.4
7.1
7.0
6.9
7.0
6.9
6.8
'7.1

7.0
7.0
7.2
6.7
6.7
7. 4
6.8
6.9
7.0
7.1
7.0
6.6
6.8
6.5
6.6
6.8
6.9
6.5
6.7
6.7
6.7
6.5
6.8
6.8
6.8
6.8
6.7
8.7
10.1
6.5
6.8
6.7
6.8
6.7
6.5
6.7
7.3
7.3
6.8
6.7
9.7



- Cl
S- O
H U
H
si
165
140
100
35
25
80
30
25
50
50
40
210
40
45
50
60
80
85
100
120
115
100
80
90
75
75
100

75
80
90
55
65
120
60
75
75
90
75
45
60
60
65
65
65
35
45
45
45
65
45
50
55
75
135
200
430
45
65
60
75
50
50
50
215
125
65
60
975


g
O
M
Cj) 00





































































OXYGEN
DEMAND,
mg/I 02

t>
u

218


185

152

351



384
468

535


556

620

612


672

681

668


637

552

620


712

603

500


471

517

512




510

381


719

396

480


524

g
II
M
CQ








































































M-§
|l
W *"*•"
1 f









































































|§
Stf








































































l»
ll
l-l "-.
Bf









































































p™
co 6





































































NITROGENOUS
COMPONENTS ,
tng/1 N

5
s

482


148

134

130



284
167

237


330

421

384


398

347

428


213

104

90


322

302

230


126

123

92




.76

22


145

220

2.3


154


„ „
ii






































































1
g

13


40

31

157



142
11

136


212

181

147


215

203

147


212

303

316'
"

286

263

162


313

348

339




392

70


551

384,

203


279


|
1

21
)

48

48

165



128
12

196


225

209

225


235 [

26?.

220

"
280

272

245


223

213

183


234

253

275




377

210


431

159 .

168


287 ,.




B *
§-^
93 U





































































1


*
1"
11







































































EM B
II
H JS
§ U
O -H
u e

4990


2490

2230

4150



5300
5380

6060


8050

7830




7560

7430

7880


6490

5260

5500


7430

6560

5420


5230

5940

6130




6180

5270


8510

5330

5150


6530

                                       132

-------
APPENDIX A-3:  page 5 of 6

DATE

11-4-70
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11

i
.TEMPERAl
•P












ac
a.
8.8
8.6
8.2
7.6
6.7
6.8
7.1
6.9
6.9
7.0
6.8
6.8

















































7.0
7.0
6.7
6.7
6.7
6.9
6.9
7.0
7,5
6.8
6.7
6.5
6.4
6.6
6.9
6.8
6.8
6.9
6.9
6.8
6.7
6.8
6.6
6.6
7.0
7.0
7.5
6.7
6.9
6.9
6.8

8.5
6.7
6.9
6.6
6.7
6.7
6.9
6.8
6.9
6.8
6.9
7.0
7.0
7.2
6.9
6.7
6.7
6.6
6.9
7.1
6.7
7.2
8.1
8.0
7.4

• •'
520
35
76
40
40
50
70
60
60
50
60
55
85
160
55
60
50
65
85
115
50
130
250
205
80
.
O
u o
M
3 *i
1 »





























































OXYGEN
DEMAND,
mg/1 02

CHEMICAL
280

227


265

332

319


301

275

266


562

245

422


470

409

405


408

438

511


406

404

375


328

375
417

460
477
383

534
479
384

384
4
BIOCHEMIC
5- day






























































.§
CA in
O X
M vD
tJ U
S5 i— '
3 ob
W E































































CYANIDE ,
mg/1 CM






























































i
Is
§n
w -*.
EC ep
H E































































SULFIDE,
mg/1 S





























































NITROGENOUS
COMPONENTS ,
mg/1 N

AMMONIA
284

382


568

588

381


465

339

185


30

129

137


20

48

73


96

157

24


56

148

.82


312

255
78

66
7.4
97

129
185
211

260

ORGANIC
NITROGEN






























































NITRATE
84

77


44

54

72


98

79

105


197

81

165


213

224

170


260

161

233


213

167

125


109

158
238

210
282
209

260
224
171

85

NITRITE
0.08

0.01


<0.01

0.05

0.13


0.31

0.03

0.02


<0.01

<0.0

0.01


211

250

250


260

279

225


200

205

130


110

180
196

190
255
175

257
195
85

30

*
&d
|g
cu
M *-*
S-~
0"
CL. f































































CHLORIDE,
mg/1 Cl





























































*
ii
CONDUCTS
micromho!
5150

4720


6490

6690

6340


6270

5440

4270


4440

3700

4150


5170

4910

5140


5720

6100

5230


4400

4950

3380


5340

5850
5600

5350
5490
5600

7460
7370
6360

7080
                                        133

-------
APPENDIX A-3:  page 6 of 6



DATE

1-12-70
13
14
15
16
17
18
19
20




TEMPERATURE
•F














s.

6.8
6.9
7.5
7.0
7.0
7.1
6.8






ALKALINITY,
rag/1 CaCOj

45
55
470
65
75
70
55





z
s «











OXYGEN
DEMAND,
mg/l 02

CHEMICAL


303

329


337

362

IOCHEMICAL
5- day
00













FHENOLICS ,
mg/l CfcHsOH














u z
Q U
If














THIOCYANATE,
mg/l SCN














S«
K-











NITROGENOUS
COMPONENTS,
mg/l N

AMMONIA


594

552


454

417

si











NITRATE


81

193


160

160
•
NITRITE


71

116


125

139
•7



\&
§t~4 •
60
B. f














CHLORIDE,
mg/l Cl


f.











CONDUCTIVITY .
mlcromhos/cm


7200

7030


6120

6410

                                       134

-------
APPENDIX A-4:  BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE  PLANT WASTES
              ANALYTICAL DATA FOR EFFLUENT FROM THE DENITRIFICATION UNIT



DATE
-,
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27 >
28
3-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3 t
4
5l
6
7
8
9 :
10



I
is-












i



































^



•


,


__ — -




EC
Cu
6.4
6.4
6.5
7.3
7.1
6.9
7.0
7.0
7.0
7.5
7.5
7.4
6.7
7.4
7.4
7.3
6.5
6.4
; 6.4
: 6.7
6.6
7.2
7.1
6.6
7.4
7.0
7.1
7.3
7.4
7.3
7.6
7.0
7.8
8.0
8.3
8.0
8.0
8.3
7.8
7.3
6.9
6.7
7.2
7.0
6.5
7.3
7.4
7.3
7.9
7.0
7.2
6.9
7.0
6.9
6.7
7.1
6.4
6.5
7.0
7.4
7.4
7.8
7.8
8.1
7.7
7.7
7.7
8.0



* 
1
J U
h

159

196

96


29

29

30


37

40

30


31

24
24

28
16
14

24
15
24

45
37

43


28

36

43


84

40

46

28

. 20

16
ii -••
OXYGEN
DEMAND,
mg/1 02

CHEMICAL



































418


















470




^
\ «
1?
j in
>
M
«



































193








*



'





105

,

• 	 —



„•&
PHENOLIC:
mg/1 CbH


























































^ ^— ^—




U 2S
S°
5^
Bff






























































«
\l
gf
































12
8

8



























SULFIDE,
mg/1 S



























































NITROGENOUS
COMPONENTS ,
mg/1 N

AMMONIA

188

179

155


193

213

220


169

147

186


157

126
151

142
116
56

74
102
131

153
197
134


227

224

176


179

265

322


147
90

71


ORGANIC
NITROGEN

45






29






43






28




24



26



34




26






35






28





NITRATE

48

14

11


0.1

4.7

1.1


11

69

56


24

14
19

1.2
28
16

2-1
1.1
52

1.1
1.4
1.4


1.4

1.7

1.7


0.5

1.0

0.6


52
38

24


NITRITE

44

15

10


0.05

2.8

0.2


7.8

59

51


13

8
16

0.01
22
10

2.7
1.0
48

0.01
0.01
0.16


0.11

0.02

0.02


0.05

0.01

0.01


53
29

35




W
isf
§**^
60
ex E






















































24







.
CHLORIDE
mg/1 Cl
































468
468

498

























^ s
t-Z.
CONDUCT I
micromho

2900

2650

2620


2860

2820

2830


2230

2370

2410


2140

2220
2510

2610
2330
1800

2270
2430
2615

2560
2970
2410


3070

3110

2830


3070

3600

4000


3550
2650

2540

                                       135

-------
APPENDIX A-4:  page 2 of 6



DATE



4-11-70
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
. 23
24
25
26
27
28
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18



1
flfi Du
s*
B






















































.



















i



8.7
8.3
8.1
8.5
8.5
8.3
8.0
7.6
8.3
8.0
8.1
8.0
8.0
8.2
7.9
7.2
8.0
8.0
8.0
8.2
7.9
7.6
8.0
8.9
8.8
8.4
8.4
8.2
7.9
7.9
7.9
8.1
8.6
8.2
7.8
7.9
7.8
7.5
7.4 '
7.6
7.4
7.0
6.7
6.8
8.4
7.8
7.7
7.9
7.7
7.7
7.1
6.9
7.3
7.3
7.1
7.1
7.0
7.1
7.3
7.4
7.5
7.8
7.9
8.3
7.8
7.1
8.1



» fO
E 1
H4
d C
1 »


475
320
460
415
385
400
290
220
460
375
420
425
375
500
375
75
385
340
360
450
425
450
475
935
1100
850
790
550
325
285
300
400
775
540
460
480
465
370
335
315
315
180
10.0
150
675
550
550
550
450
450
280
190
260
240
210
220
205
230
260
290
310
380
375
450
340
220
275


1
o o
^H
3 -*•
i $


65

44

30


44

68

290


102

129

110


41

40

159


82

55

44


166

65

15


32

23

53


53

50

67


61

60

76


75

20

OXYGEN
DEMAND,
mg/1 02
j
u
tj
U























1000



























1590















520

w ^
S *
a -a
a























141



























734




















«l
^a u
g ,_,
£* W








































































af z
5 u

If








































































§ £§
fn VI
o *-•
fSf








































































»
£-1 Cfl
fi-
g's
01 6





































































NITROGENOUS
COMPONENTS ,
mg/1 N

I"H
§
1


112

189

139


391

626

882


980

875

595


52*

616

1170


812

343

966


1550

1210

490


273

371

1190


1610

812

469


196

160

176


82

90

US
^^ 55
§ §
Is


28






28






62






70






43






59






49






78






14






20



1

s
g


35

0.1

82


141

124

66


58

189

339


328

376

22


0.1

0.1

0.1


0.1

0.1

0.1


44

8.1

0.4


0.1

0.1

0.2


0.1

0.2

0.2


0.1
,
51
!

s
K
s


43

0.05

11


169

124

> 85


92

229

293


405

357 '

16


0

0.02

0.01


0.01

0.02

0.01


93

9.1

0.01


0.03

0.03

0.03


0.05

0.06

0.02


0.02

40




jV
35 CM
C/l *-<
8»













,
i




i



16



























36




















.s-
" W O
§ ~-
it







































































>-" 8
H u
> a
y K
a u
ll


3440

3570

4700


7230

9000

10300


10180

11100

10810


11800

11200

12500


7920

4210

9560


3100

0500

5240


4000

5070

0700


4000

7130

4710


2480

2270

2340


2190

2700

                                         136

-------
APPENDIX A-4:  page  3 of 6



DATE



6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
H
12
13
14
15
16
17
18
19
20
'•• 21
22
23
24
25
26



L

*
H










i



33
CL


8.5
8.8
8.9
8.6
8.7
8.7
b.b
8.5
8.5
8.8
8.')
9.0
!










































MI i ' —
9.0
9.3
9.0
8.4
7.9
7.5
8.3
8.3
8.6
8.5
8.6
8.6
8.4
8.8
8.6
8.4
8.5
8.8
8.3
8.2
8.5
8.4
8.2
8.2
8.1
7.9

6.9
6.7
7.3
6.6
7.0
7.0
7.2
7.5
7.5
8.0
7.6
7.9
7.7
7.8
7.8
7.8
7.5
6.9
7.2
7.6
7.8
7.8
6.5
6.9
8.2
8.2
8.1
7.6
7.3
7.6
	 im



" to
El
g «

3 F?
M B
425
500
575
430
560
525
570
380
400
560
450
620
600
525
875
480
300
280
450
400
565
520
540
540
475
515
450
385
520
745
375
385
475
460
500
515
460
370

270
245
250
250
225
210
235
280
340
415
315
285
305
345
375
360
260
240
155
210
280
295
40
50
435
405
350
325
310
350


i
u u
•4
5 v"4
< "^
8 i
o s
73


32

13

7


10

26

35

















292

















150





OXYGEN
DEMAND,
ng/1 02
3
a

H
U
313


184

515

367


390

487

504


565

409
469

464
392
466

437
410
504



1400
1140

494
573

262

360

292

596

322

67

933


743

691
^
-» x
S3

g"1
3



















266















189























OLICS ,
C6H50H
S5 i— '
1"5
a ff























































•"—



ta 55
O U
H
2 _<
!"»
s t























































"



CYANATE,
SCN
o <-<
H *-*
T* fj.
H i



























































S'o,
E i-4
i"«
w 5























































—
NITROGENOUS
COMPONENTS ,
mg/1 N
g

XJ
*

190


133

202

94


132

92

164


265

228
216

204
190
281

330
308
759



1170
750

174
146
148


182
171

78


113
124

85


209

258
" —
0 S
si
< ft!
S S
o z



26






27






30




30



34








21




22





16





24



B

H
Z
3


45

158

96


48

129

0.3


0.2

20
3.8

7.2
35
2.0

0.3
16
0.1



0.2
0.4

0.2
0.1
0.3


0.1
0.3

0.1


0.5
40

0.3


0.1

0.2

§
OS
a
rH
z
2.8


47

14

120


52

130

0.02


0.03

24
4.4

7.3
31
3.4

0.01
19
0.01



0.01
0.06

0.01
0.01
0.47


0.02
0.09

0.05


0.01
43

0.01


0.01

0.08




Id"
I2"
CO **
Q "^
a, f

















33

















39























H U

S 00
U S


























































»T e
s|
•4 O
~* *S

5 U
' "rf
U E
3800


3930

4320

4480


4540

5320




3760

4330
4360

4140
4400
9300

4670
5180
8910



10800
7540

2600
2390
2360


2570
2580

1760


2030
2150

2200


2980

3500

                                           137

-------
APPENDIX A-4:   page 4 of 6



DATE

8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
1 '10- 1-70
2
3
4
5
- '&'
7
"'8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
... 28'
" 29
30
31
11-1-70
2
3



3*
H








































































35
B.

7.3
7.4
7.4
7.3
7.7
9.0
8.0
8.2
8.6
8.5
7.7
8.5
E.8
8.6
8.5
8.5
8.5
8.5
8.5
8.4
8.4
8^3
8.2
8.3
8.4
8.3
8.3

8.4
8.2
8.3
8.5
8.5
8.5
8.7
8.9
9.0
9.2
9.0
8.7
8.6
8.2
8.3
8.4
8.4
8.0
8.5
8.8
8.9
8.9
9.0
9.0
9.1
9.1
9.2
9.2
9.5
9.2
8.8
9.1
9.1
9.1
8.9
8.9
9.0
9.4
9.0
9.0
9.5



- C*l
>< O
s 3
•s °
I "
s3 *
295
290
300
305
390
675
350
500
475
550
925
590
760
665
675
710
800
875
775
740
700
750
580
640
725
675
715

660
575
550
640
625
650
700
750
710
780
830
725
775
650
650
640
700
700
780
830
960
1045
950
930
1000
980
925
835
920
1175
1000
1035
1435
1225
900
775
900
1020
1005
950
1200


§
a °
s<
i f





































































OXYGEN
DEMAND,
mg/1 02
a
o

629


544

456

468



563
605

684


558

657

596


1350

605

668


691

626

788


931

690

587


683

1750

1130




792

1130


1015

587

926


974 .

H X
w "O
O lA
5


















136
















































362




-g
SS
M VO
^ °
|~
It








































































gg
§=:
ff U)
u I








































































IOCYANATE
/I SCN
gf








































































1:
M e





































































NITROGENOUS
COMPONENTS ,
mg/1 N
jjjj
1

479


255

112

119



254
167

208


296

386

378


367

367

414


207

137

64


202

258

252


204

148

116




55

120


190

207

1.1


160

GANIC
TROGEN
8 £




25







33





43






172






40






375






60













42






97

1
g

0.2


0.2

0.2

17



0.2
11

15


0.4

2.9

18


17

40

57


67,

99

80


115

.114
i.
22


3

45

78




131

8


1.4

11

33,,


15,,. .

1
w
•z.

0.18


0.03

0.08

21



0.15
12

18


0.04

2.9

31


18

44

75 ,


79

58

66

:''
64

74

8


2

24

46




126

11

f
0.07

1.18

38


17




W v-l
sc M


















10

•


















12



























; 11




a-
H U
O r->
3 &p
U 6







































"*














i

^








i
T




X E
OnXJCTIVXT
cromhos/ci
O -ri
a 6

5050


3280

2060

3320



4230
4490

5020


'5720

6520

6520


6580

6750

7320


5990

5100

4540


5630

6070

5150


4720

5300

5780

t •
»

5880

5270


6440

5600

4480


5590

                                         138

-------
APPENDIX A-4:  page 5 of 6

DATE

11-4-70
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-70
2
3
4
5
6
7
'8
9
10
11

1*
E




,























































X
a

8.8
7.8
7.0
7.0
6.9
7.0
7.1
7.6
7.5
7.6
7.8
7.2
7.5
7.3
7.7
8.0
8.0
8.1
8.5
8.8
8.7
8.1
8.5
8.1
8.5
8.6
8.9
9.0
9.1
9.2
9.1
9.1
9.2
9.0
9.0
8.9
9.1
9.4
8.8
9.5
9.3
9.2
8.8

7.6
7.6
8.0
8,2
8.3
8.5
8.8
9.0
9.0
8.9
8.8
9.0
9.4
9.4
8.7
8.7
8.6
8.6
8.8
8.7
8.4
7.6
7.8
7.8
7.9

- en
e s
S 5
M
d ***
i f
1130
655
420
280
250
300
350
410
420
470
495
470
525
520
525
575
560
550
675
675
550
395
480
525
490
560
700
660
680
730
705
930
915
930
860
840
775
825
990
900
820
840
840

830
650
575
575
575
680
850
88O
860
780
700
710
850
1025
535
760
775
875
950
840
740
500
425
380
330
,
s °
i ~
% %



























































OXYGEN
DEMAND,
fflg/1 02
§
1
1160

1350


864

1000

1020


1090

935

675


624

613

456


500

546

501


672

556

560


575

594

863

755
582
755

575
544
600

773
707
706

508
3
Sa ^
W "O
o in
s

































245




















276





-g
8£
H \O
J O
it




























































§g
Z -t
<-**
Bf




























































B
§5
S-*.
«
H I




























































Q tn
5 60
« t



























































NITROGENOUS
COMPONENTS,
mg/1 N
g
i
246

386


599

596

515


465

440

249


87

98

157


78

62

81


136

185

46


102

99

2.2

241
249
73

64
4.6
86

118
176
210

594
O w
ii





50






18






43






31






34






32





41



84



160



34
g
g
0.6

0.5


0.2

0.2

0.3


0.3

0.2

0.4


19

66

9.6


24

62

58


1.1

36

45


.2

.2

.4

.4
.4
.1

39 .
42
54

2.1
18
.4

4.0
|
i
0.01

0.01


•co.oi

<0.01

•oo.oi


0.01

<0.01

<0.01


<0.01

.07


-------
APPENDIX A-4:   page 6 °f 6



DATE

1-12-71
13
14
15
16
17
18
19
20



3f













X
CU

6.8
7.3
7.5
7.8
8.0
8.1
8.2





ALKALINITY,
mg/1 CaCOj

250
375
470
600
640
525
625




|
O
s ^
u ep










OXYGEN
DEMAND,
mg/1 02
CHEMICAL


786

743


641

590
IOCHEMICAL
5-day
CQ












PHENOLICS ,
mg/1 C6H50H













CYANIDE,
mg/1 CH













THIOCYANATE
mg/1 SCN













SULFIDE,
mg/1 S










NITROGENOUS
COMPONENTS ,
mg/1 N
j


605

529


440

403
ORGANIC
NITROGEN







36


NITRITE


.3

.3


.3

.3
NITRATE


.24

.02


.04

.32



PHOSPHATE,
mg/1 P04













CHLORIDE ,
mg/1 Cl









-


!w B
CONDUCTIVTT
micromhos/CT


6840

6800




6160
                                          140

-------
APPENDIX B-l:
               BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES
                   ANALYTICAL AND OPERATIONAL DATA FOR THE CARBONACEOUS UNIT


DATE









2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
11
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
nmiUD Ln
LIQUOR
ml/1500
gal.

J
**
22
n"<
2
^
LI









































1 W
i— < U
X CO
3 Ou
.0 91
-H O
M •£•








































TO BIOLOGICAL
pounds /day



QJ
C
O
4J
w
* CN
o °
t4
"Q D
OJ jj
> -rl
t-4 i— «
O '^
w 00
» E
•l-l
o









































t£
ft *^
c: •*-*
3 w
o c
•a a
3 U
O >J
^ OJ
aa a

























2















W
C
(0
Q

»!-*
(J

)
C/i






9 1/4
7 1/2
7 1/2
7
8
9
7

7
7
6
6
6 1/2
71/2
6
6 3/4
7
7 1/2
7 1/2
61/2
7 1/2
10 1/2
8 1/2
9
9 1/2

10
14
12
12 1/2
8 1/2
11
14
9 1/2
RETURN
SLUDGE


„
£ *
o 
-------
          APPENDIX:B-1;   page  2 of  10


DATE









3-12-70
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
t\i Ifiwt xn
LIQUOR
ml /I 500
gal.
U

M
JS
a u
(Q *<3
O
£





















750


















1 0)
^4 i>
X <8
3 O.
.a w
i-l O
££




























30





50




TO BIOLOGICAL
pounds/day




o
w
at
E






1
I
1
































B
•H
,-)
4J
C
^1
3









































ID
to
1J 4)

£4 *F-j
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£
















2



1/2



















OJ
iJ
E§
3 O

*O ^
o m
w o








1



1
1


2
2




2
2
I







-






BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /min.


"c3
u


o ^
*4H i— <

O — '
j3 (•>
a

73.0


69.0

18.0

60.0


61.0

65.0

85.0


56.0

67.0

85.0


30.0
25.0
25.0
24.0
28.0


50.0

26.0
25.0
50.0
89.0

to
,— I
O
CO
"O fl)
lit 1J
•a TJ
C ^-t

a. u>
m £
3
en







































e

-------
          APPENDIX B-l:   page  3  of  10



DATE









4-20-70
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
LIQUOR
ml/1500
gal.

J
*
*
) *O
• *H
1 «£
J
£
































750


750
750


1 w
I— « u
>> a
»•§.
J3 01
-H O
H£



,•

100




125



125
















50
100


125
125
TO BIOLOGICAL
REACTOR,
pounds /day



CU
C
o
w
CU

J






































o
6
•H
rJ
4J
e
M
s








































*t3
(U
q g
•0 J
£







































u
u
CO
3 O
•H .0
TJ M
o rt
CAU





































BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /min.


r-4
flj
U
[Q
W iH Id
W C O
 -rl
r-l i-4
O "--
u) E
a


























3.1


2.25
3.1
4.0
4.8
3.0


4.1




CD

C -^

O C
•a 41
3 u
O k
r-1 41
to a.
2































2
2
2



in
a»
•ill
c c
. Oj '-H
H
. a' u
O in
•M Q
EC
4-1 «r4
C J=
(U 0
E u
•r* CU
•Q c/1
0)

3 1/2
3
3
3
3 1/2
4
3
4
3
4

3
3
3
2 1/2
3 1/2
3
2 1/2
4

3
3
4 1/2
4
5 1/2
4 1/2
6
3
3
3
4
2 1/2
3
3 1/2

3
4

RETURN
SLUDGE


' *•
„
C V4
O a

•rl

O ^1
"2
w
262.0

412^6

740.0


400.0



400.0


250.0

325.0

600.0


600.0

623.0

725.0




785.0
300.0


400.0

350.0


Cfl
T3
O
to
T3 41
Q) 4J
•a .^
C ~H
41 ~~.
, a ^i
3
tn





































SPECIAL
CONDITIONS


Q
U
jjj


kA
C
1
O
b

X
X
X
X
X

X
X


X
X

X




X




X





X








00
2*
•d
^
r-l
3
CO

01
I
p^
t/J







































V
00
•o
_< (U
*W
00 "-<
c n
t-i CO
*J r-l
go

a.

X






















X















OPERATIONAL NOTES









Reestablished 27. daily blowdown.



Sludge recycle, 0.9 gptn.

Waste flow off,








Haste flow off ? hrs.

Out of T.B.P.












Power off, 40 min.; Emergency air on.
Waste flow off.lO hrs.





Waste flow only, 0.5 gpm.
CO

-------
APPENDIX B-l:  page 4 of 10


DATE










5-28-70
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
It
CHEMICAL ADDITIVES
TO EXCESS
AMMONTA
JWlVKllA
LIQUOR
ml /I 500
gal.

U
•
M
O tJ
.C i-t
0* U
01 ^Q
o
£


560
750

750

0

750

750
600
530
490
510
490

750

750



750

0
750

750

750



750

750



1 V
^•4 ^
^ J3
3 a.
^ CO
•ft O
^£


100
125

150

0

150

150
125
125
98
75
100

50










1OO

100



100

100

TO BIOLOGICAL
n^ Hf*mr\D
KEAL i UK ,
pounds /day



(U
o
4J
ID
i
E
T-l








































tu
E
4
J* E
•S
15O.O
175.0
175.0
214.0

140.0
130.0
160.0
180.0

100.0
100.0

80.0
75.0
70.0
60.0
150.0
75.0
43.0
42.0
50.0
58.0



40.0
42.0
57.0

37.0


50.0

60.0

50.0

m
•o

O
k*
•0  T*

o — -
v> t>o
m c
0
3.0
3.1
3.0
2.1

2.25














0.2
2.4
2.7

2.7


2.0
1.5
3.1
1.4
•1.8

2.3
1.3
2.
1.8




5?
" -Q
C ^
0 C
•o 01
3 u

*-< 
-------
APPENDIX B-l:  page 5 of 10


DATE









7-5-70
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
11
12
CHEMICAL ADDITIVES
TO EXCESS
&MATWT&
aSfmfRJatA
LIQUOR
ml /1 500
gal.



s
'<5
-


750

75O

750


750

750


750

750


750
7 SO
750


750




750

750

750


750
750

«
,~i u
M
9 O.
s a
J J
H »•

100

100

100


100

100


100

100


150
100
100


150




150

150

150


150
150
TO BIOLOGICAL
REACTOR,
pounds/day





S
1
6
^ .






































41


•U
C
3
»







































•o
u
4J Q)
53

33







































*»
E 8
35
D M
O 01
eno





































BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /ntin.



*-«
U

>\ CM
o °
Vl
at 4j

o ^^
m t>o
43
O

3.0
1.8
2.0
1.9
2.0
2.6
2.3
2.7
2.7
2.0

2.1


2.5
2.4
2.6
0.1
2.2
2.0
1.5

1.9

2.3
1.8
0.8
2.3
2.4
1.4

1.9







&
»tj

•a at
S o
O Vl
^ 01
m a.

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
O








2
2
2
2
2
2
2
2
2
2
2
2

0)
4}
B C
^ ^
C u
o in
-r< -rt
*j a
0
•a
3 ^
(O -H
hA .-J
if I.
•** a
1"





X
X











X








X

X











OPERATIONAL NOTES




















Waste feed off 2 hrs.











Waste feed off, 2 hrs.
Waste feed off, ? hrs.









Sludge recycle rate; 1 gpm.

Sludge recycle rate, .85 gpm.
Sludge recycle rate, .67 gpm.

-------
APPENDIX B-l:  page 6 of 10


DATE












8-13-70
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
£U UrlUn Ln
LIQUOR
ml/1500
pal
gel .

y
•p4
O "0
«£• ^
£•«
B •<
O
J?


750


750

750


750

750

750

750


750

750

750



750


750

750

750

750

/
750


1 01
r-4 U
>> a
u ^
3 CL
J3 tO
•r4 O
M *£
E-i fc

150


150

150


150

150

100

100


150

100

150



150


150

150

200

200


200
TO BIOLOGICAL
REACTOR ,
pounds /day




01
c.
o
&J
m
fU
6
•H
,j








































4)
J


4J
CJ
>4
3
«










































•o
4J ^J
2 ^

T) >J
^
*









































— i
d
u
at
(fl -H J-i
w c c
a) o 3
o g c

W  -r4

& ^^
in oo
n S
«H
Q



2.1
2.5
.5
1.8

1.2
1.3
0.9
0.7


3.0
2.0
2.4
1.5
1.3
1.3

1.0
1.0
1.5

1.1

1.6
0.57
0.3
1.4

1.6
0.86
1.7

1.3
1.0
1.4



-1

c ^~
o c:
•a  O
E o
•3 ni
•a to

CO

2 1/2
3
3
3
3
3
2 1/2
2 1/2
2
2
2
2

2
1 1/2
2
2
2
2
2
2
1 1/2
3
2
1
2
3
1 1/2
1 1/2
3
3
2
2 .
1
1
1
2
2
2
RETURN
SLUDGE



•*
s *
O Qi
O 4J
•H
H | ••^
o ^
•C E
e
M


250.0


123.0

170.0

209.0


250.0
200.0
218.0

200.0




233.0

200.0


327.0

407.0

250.0


180.0

210.0

180.0



•r*

0

•O Q)
0) U
C i~i
a) "--»
0. 00
01 E
3
CO








































SPECIAL
CONDITIONS

H
o
4J
U
cfl
Q)
Cd

H

E

O
fe





















X

X
X

X
X
X
X
X



X






00
C
•r-4
^
13
CO
• V
00
•o
3
t-4
cn





























X
X










a)
"O
3 *j
.-( (U
en *F*

oo -^
c n
•H n)

So


pt*










































OPERATIONAL NOTES

















System off, 1 1/2 hrs.
Waste feed off,
Reduced aerator volume; on 707. waste.
Waste feed off, ? hrs.

Waste feed off, ? hrs.

Waste feed off, ? hrs.
Waste feed 70%.



Waste feed off ? hrs.




,

Waste feed off ? hrs.
Waste feed off ? hrs.

Waste feed off ? hrs.
Ammonia odor over aerator.


Waste feed off 1 hr.



Much less foam.


Waste feed off, 45 min.

-------
APPENDIX B-l:  page 7 of 10


DATE









9-21-76
22
23
24
25
26
27
28
29
3O
10-1-70
2
3
4
5
6
7
8
9
ie
11
12
13
14
15

16
17
18
19
20
21
22
23
24
25
26
27
28
CHEMICAL ADDITIVES
TO EXCESS
LIQUOR
ml /1 500
gal.

1
1 *O
1 **^
i <;
»
*
750
750


75O

750


750

75O


750
750



750










750







750

AS
*^ fflj
J J3
3 O>
,fi. «0
•< O
ftfi
200
200


200

150


200

200


200
200



100










100







150
TO BIOLOGICAL
PPAPTflP
KtAv/ivJK ,
pounds /day



S
o
4J
n
g
E
i-t
»4








































4)
a
n4

C
14
m








































•o
0*
•U 0)
2 5
"O iJ
£








































0)
„ 2
E C
3J
•o ^
O nt







































BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals, /miiu



"«
u
n)
(fl *r4 ij
OB C 0
0) 0 3
O E D










































e
o

^ 01
1 ni
S3







































MIXED LIQUOR


Eu
01
9
4

0)


92
89

87
90
89
84
78
75
80
78
83
84
87
88
90
87
88
68
72
78
78
78
77
78

75
74
74
75
75
75
79
81
78
80
92
86
78



«•
c u
32

*M r*
o -•
£ E
S







100.0

65.0

30.0


21.0

8.0
7.0
14.0


4.0

0.6


3.0


1.0
4.0
3.5
4.0
1.2

1.5
2.5
10.0
13.0
.
•o
•H
O
cn
•S2
•O -ri
C f-t

oi 15
cn




640


760
































G
0)
60
>» CM
o °
•O 0)
fr **4
^4 «— *

T3 T*
C r-4
at *^.
O. w)
3
CA







































SPECIAL
CONDITIONS


o
u
01
on
c
1-1

Q
fa








X

X
X


























X


t*
^
f-4
3
OQ
01
60
-o
3
r-4
tn





































X



H)
•5 M
•-I 01
CO — <
l-l
•^•1 (f
4J r-l
go
(^










































OPERATIONAL NOTES









Waste Feed Off, 45 rain.

Daily data sheet missing.






Waste feed off ? hrs.





Waste feed from 70% to 50%.
Affluent, very dark color.
Waste feed from 50% to 25.






Waste feed from 25% to 15%; reseeded
system.












olidg lighter color, waste feed

-------
            APPENDIX B-l:  page 8 of 10


DATE











29
: 30
31
11-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
CHEMICAL ADDITIVES
TO EXCESS
LIQUOR
ml /1 500
: gal.
u
V*
to
(J T3
*G "»"*
o< o
to ^j
o
;?
04


750



750
750



750


750


750


750






750





750




750

1 O
i— 1 4J
•^t HJ
*•* £
3. 0.
J3 0}
•H O

E-r fo


150



150
150



150


150


150


150






150





150




150
TO ^ BIOLOGICAL
1 REACTOR ,
pounds/day


' 0)
c
o
u
. w
1>
3
•l-l
J







































01
3
*H
i ^

4-1
C
M

m









































•^3
V
u 4)
RJ I?
M f-l
t3 nJ
^
5S








































4J
4J

0 C
3 O

•O h
O (8
CO U







































BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /min.

^
cQ
U

3

«J
VI
01
o.


tH
71
71
70
75
73
67
67
64
69
75
80
78
72
73
73
78
71
67
61
69
75
75
75
74
78
72
62
65
75
78
79
80
79
80
91
90
89
90
90


d" b
O 0>
CJ -W

t4 (—4
43 ^^
o «-«

0
H
10.5
20.0


15.5
15.0
10.5
11.0



15.0

4.5
4.5
4.0


1.7
1.5
1.3
1.5
1.0
1.0

1.0


1.3
2.5
3.5
3.5
4.0
10.0
12.0
75.0
75.0
65.0

CO

M
01

>r^
t-»

be
e



280


220

















100






140









I
5>\ CM
o °-
T3 V
d) *J
> •-*

o ^-
m bo
tfi G

a
1.3
2.4

2.3
2.5
6.6
2.6
3.3
2.7
1.6

2.2
1.8
1.94



1.2
3.0
2.6
2.4
2.O
2.7
2.8
2.5

4.3
1.4
2.9

2.6
2.6
2.6
2.4
2.3
2.0

3.1
3.1


« -o
d ^.
3 u
0 d
•a at
3 u
O M
t-* a>
to a












'




























v>
01
IS
C u
O to
•H- -i-(
<6

C X
a) u
e o
•H 4)
•X3 C/3
Q)
Cfl

2
2
2 1/2
1 3/4
2 1/2
3
2 1/2
2
2
2
2

1 1/2
1 1/2
2
2
1 1/2
2
2
2
2
3
3
3 1/2
3

4
3
3
4
4
4
4
4 '
3 1/2
9
3
4
3
RETURN
SLUDGE


„
d ^
o o>

.
ii | |
IW *^.
O ~*
£ e

^|


15.0


20.0
22.0
21.0




10.0

15.0
9.0
3.0


1.6

1.0

15.0
1.0

1.0

1.1

3.0
10.5
5.5
5.0
5.0
11.0
80.0
130.0



tn
•a
o
c/5
"O nl
01 W

d ,-<
41 ~^.
O- 00
w ^
3
CO








































SPECIAL
CONDITIONS

M
U

-------
            APPENDIX- B-l:  page 9 of 10 "


DATE









12-7-70
8
9
1O
11
12
13
14
15
16
17
18
W
20
21
22
23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
12
13
14
CHEMICAL ADDITIVES
TO EXCESS
LIQUOR
ml /I 500
gal.




"^

. u










750

750



750


750



750

750



750


750

750



750



01
r*i *J
»* ti

3 O.
.a m
•^ o
E-i tt<









150

150



150


150



150

150








150



150

TO BIOLOGICAL
OPA/^rP/M3 '
K£i At> i UK ,
pounds /day



OJ
c
o

01
0)
e
•H
J








































0)
3
1-1
pJ

U
C
M
3
CO










































"O
0)
4J a
CQ E
M -r1
•Si"
X









































cu
4-1
fd
E c
D 0
•H JJ
•a M
o «
VJ O







































BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /tnin.


F—4
(fl
y
(U
01 'ft |ri
W C O
0) O 3
o i u
w< ^











































c
o
•l-f M
4-> 0)
r-l fl)
0







































MIXED LIQUOR

fa
o
0)
^i
3

a
M
a>
H
87
88
88
87
91
92
91
91
89
92

86
85
85
84
82
84
90
88
93
90
86
83
88
88
88
87
86
90
95
97
95
95
96
87
85
84
85
86


 "r^

o ^^
ta &p
w g
•H
a
3.3
4.1
4.1

1.6
2.3
1.8

2.4
2.6

.86
2.0
1.9
2.3
2.3
1.8

1.8
2.3
1.8
1.7
2.3
1.8
1.9

2.4



1.7


1.9
3.1






S"
** *o
c -^.
9 u
o c
"O O)
0 U
pa o.









































tn
(U
G S •
u
(0
•H
o

ip4
f-t
CJ

a)
en

3
4 1/2
3 1/2
3 1/2
31/2
3 1/2
3
3
2 1/2
2 1/2

3
3
3
3 1/2
3 1/2
3
3
3
3
3
3
3
3

3
21/2
3
2 1/2

3
2
2
3
2
2
2
2
2
RETURN
SLUDGE


„
C M
o W ***
r

78
150.0
250.0
275.0
425.0

250.0
250.0
540.0
450.0

400.0
3OO.O
400.0
225.0
350.0
400.0
350.0
375.0
350.0

450.0
450.0
350.0
450.0
440.0
430.0

593.0

450.0

425.0


408.0

725.0


in
.-*
O

TJ at
a u
TJ -r4
C r-4
3) •"»*
ft?








































SPECIAL
CONDITIONS

O
u
(0
01
fV*

00
™

•rH
1



X
X
X

X






























X



S
j;
3
EQ

01
r\H
•D




X









X
X























X

at
00
P M
,-< at
m
bO *H
& Lj
•rW C3
^1 r^
(B O
O
«— 1










































OPERATIONAL NOTES











Waste feed now 50%.








Waste feed off, ? hrs.


Waste feed off, ^ hrs.









"
Waste feed now 25%,

Waste feed off, ? hrs.

Jaste feed now 35%.
Waste feed off,
Waste feed off,
aste feed now 50%.

Waste feed off,
aste feed reduced intermittently.



VO

-------
            APPENDIX B-l:  page 10 of 1O



DATE


1-15-71
16
17
18

CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
LIQUOR
ml/1500
gal.
Phosphoric
Acid


750


Trlbutyl-
Phosphate


150


TO BIOLOGICAL

pounds /day

Limestone





*•
la
c
i





Hydrated
Lime





Sodium
Carbonate




-
BIOLOGICAL REACTOR
INFLUENT

gals. /min.

Excess
Ammoniacal
Liquor



-


Dilution
Water





MIXED LIQUOR


O
V
3
a
!
H
86
90
89
89
i'- '


Imhoff Cone,
ml/liter
250.O


270.0

ra
>u
•H
Suspended So
mg/liter





G
0)

Dissolved Ox
mg/liter 0







Bloudoun,
percent/day






(0
V
.£
CD -rt
C 0
O 01
Sedimentati
Secchi Di
2 1/2
3
2
2

RETURN
SLUDGE



^
Imhoff Cone
ml/liter
450.0


490.0




-------
APPENDIX B-2:  BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS RROM COKE PLANT WASTES
                    Analytical and Operational Data for the Nitrification Unit



DATE





2-1-70
2
3
4
5
6
7
8
9
10
11
12

13
14
15
16
17
18
19

20
21
22
23
24
25
26
27
BIOLOGICAL REACTOR
Influent
low Rates
gpm

$ I

0 C
M
1





























o

1






























CHEMICAL ADDITIVES
Daily Dosage
Pounds

1 S
•*•* tfl

§ tn































s
s

I
J

i




2
2
1

1
3

2

2
2












«
j

c
3
ta







1
1/2

1 1/2



- 1/2
2 I/
2 I/
2
2
2

2
2
4
4
4
4



-o
e
(B 01
* i
^ »*
x



























3
3

IS
— o

0





























llliltters
u
5^

P
L,






























S.5
a Q.
3 B)
HO.





























Sodium Hydroxide
Feed Solution
Volumetric
Composition
o .

S ~i
S































? a
3






























s a

•o -t
V **
v e
[X





























MIXED LIQUOR

u,
41
t-i
i
^
t
H
90
78
72
75
92
85
80
84
81
77
80
83

77
82
85
76
78
81
84

82
80
80
73
82
90
80
82




X
o.

6.6
7.0
6.7
7.2

6.8
7.7
7.5
6.9
6.9
6.7
6.6


7.3
7.2
7.3.
7,4
6.9
7.2

9.6
6.8
6.9
7.1
6.8
7.0
7.2
6.4


>, (^
c n

J£ ' —
< S?
119
102
63
95

55
150
126
86
111
123
127


205
178
174
138
135
166

130
125
140
115
120
170
174
90

0*
•a ^.
1 =
in a*

o































u
c
O f
o u

0 -~
"
10.0
4.0
3.0
2.5
5.0
4.5


4.0

10.0
5.5

5.0
5.0
3.5
5.5

4.9
5.0

6.0

7.5
9.O

9.0

8.5



t

































IS
U
c
-
«
X
y
u
(Q






4
4 1/4
3 1/2
3
4
4
31/2


3
3 1/2
3 1/2
4
3 1/2
4 1/2

4
3:1/2
4 1/2
5 1/2
6
4 1/2
4 1/2
5
Return
Sludge




Is
o ~~

% "e




0.75

7.0


11.0

12.0
8.0

10.1
	
10.0
17.0

15.0


13.0

19.0
25.0

22.0

15.0




t
































Special
Conditions

u
o
1
f

£































no
S
S
ta
V
W)

w































M
"O
3 n
»3
NJ id
Sy




































OPERATIONAL NOTES




Sludge recycle 1 gpm.


Reactor off 45 min.







Attempting to maintain PhS.alk-
200


Sludge return problem



Rising sludge noted during Imhoff
cone test




Mixer and air off, ? hrs.




-------
               APPENDIX B-2:
                             page  2  of 12
Ui
to



DATE




28
3-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1
2

Influent
Flow Rates
gpm

3
S *j
asg
1* -
<0«
3
u
k
I
^
b 1/2
J
i 1/2
)
5 1/2
21/2
3
>
1/2

L
1/2
1/2
1/2
L
1/2

1/2
t 1/2
1/2
; 1/3
) 1/2
L 1/2
1/2

" 1/2
1/2
1/2

Hllliliters

u
iL
r





































~r4 O
£•< a.


































Sodium Hydroxide
Feed Solution
Volumetric
Composition
g .
g
•n

































2250

V «-"
u tg
S"

































30


Of
S |
£ •


































MIXED LIQUOE

u.
*
01
3
01
t*
85
87
84

87
84
84
82
80
81
84
84
78
74
79
80
83
82
79
88
8O
80
70
83
83
87
81
81
86
81
83
86
88
75





O.
7.1
7.0
6.9

6.8
7.3
7.5
7.6
7.2
7.1
7.2
7.7
7.0
7.1
7.2
7.5
7.5
6.7
6.6
6.9
7.0
7.1
7.8
7.3
70
7.2
7.0
6.9
7.2
7.1
7.1
7.2
7.1
6.7



£" 51

a —i
1 t
123
117
103

75
16O
162
193
154
145
153
146
12O
no
105
158
147
108
118
98
127
145
162
ISO
103
113
92
93
145
160
139
148
170
105

(M
o
Jnli
•o *•*
Is
••< Ml
o >•





'































0)
c
O k*
U V
P


8.0

7.5

7.O


8.O

9.0

9.0


16.0

18.0

15.0


21.O

24.0

2.0


21.0

25.0

a
•O

O
T,
|f
(0



































•si
a u
c
O "
4J 00
a -H
li
0) 0)
in tn
6
51/2
6

6
8
8 1/2
10
8
9
10
7

8
9
7
9
.O 1/2
.0
9 1/2
8

4 1/2
6
7
7
5
6
6
5
5 1/2
5
5 1/2
6 1/2
Return
Sludge


*

o ».
|C
3-


18.0

40.0

24.O


23.0

23.0

20. 0


36.0

52.0

33.0


44.0

45.0

43.0


47.0

66.0


•
-
u?
•o
1 *
1


































Special
Coo**1 *•*«•««

L>
o


g
1




































S
-r<
.K
n
9
3
«



































0
3 U
to ^i
g"*
i-J 0>
E







































OPERATIONAL NOTES




























Recycle pump off, ? hrs.








-------
             APPENDIX »-2:  page 3 of 12
in
lo



DATE




3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
2O
21
22
23
24
25
26
27
28
29
3O
5-1
2
BIOLOGICAL REACTOR
Influent
Flon Rates
SP™

u c
•a





Off


























ta
V
3





i
l
i
1






















CHEMICAL ADDITIVES
Daily Dosage
Pounds

is
IS
P





12
12
12
12























o
I. limit































I
•rl
•1
e
b
































"g
||
































E •
Sodlui
Carbonj














2
1
2
2
2
2
2
2
2

2
2
2
2
ll/

4
lllillters
i
>






150

ISO
























^ tt
s-s.
.0 (B
HI





4





6
None
6
3
3
3

2
2

2

4

4

5
7


Sodium Hydroxide
Feed Solution
Volunetric
Composition

-
K~m
g
m
4000
45OO
50OO

3OOO
40OO
50OO
60OO


7OOO

50OO
7OOO
7000
7000
85OO
10OOO
125OO
5000
20000



17500
18OOO
18OOO
1800O
18500
18500

••j
« w

40
40
40

40
40
40
40


40


40
40
40
30
4O
40

40



4O
40
40
40
40
40
at
*j
M C
f 5
1 •


100
















75

70



110

110
9O


MIXED LIQUOR

it.
\
0
H
H

81
82
95
84
85
85
88
88


90
88
90
92
93
93
90
89
90
93
94
94
94
94
94
95
97
97
90
84




S

7.2
6.9
7.3
8.1
6.8
6.6
6.4
6.8


7.2
6.5
6.2
7.3
7.1
7.5
6.9
6.9
6.9
7.3
7.3
7.4
6.7
7.4
7.0
7.8
7.5
7.4
7.1
7.4


£ ff
2 "i
•*« U
h

120
80
85
230
65
25
35
70


60
45
5O
77
85
170
57
77
6O
100
150
160
55
105
100
160
163
197
90
20O

(Nt
0
TJ *^
o -
« c
« «l
ss
3




























~*




£

P

28.0


38.0

30.0

22.0


26.0

38.0
20.O
20.0
25.0

26.0

31.0

24.0


22.0

26.0

25.0

•0
^
O
w
•0

01

























640

380

830









6 1/2
5
5
4

8 1/2

9


9
7
9
8
5 1/2
4
41/2
6
5
5
5
5
5
4 1/2
5
4
5

4
4
Return
Sludge




e

P

52.0


62.0

72.0

55.0


51.0

27.0

58.0


75.0

38.0

50.0


34.0

75.0

30.0


M
•a
2
in
•a
0) r-t
C 00
g. f
Ul































Special
Condition

n
o
i
2
1



X
X

X




X







X

X




X


X
X



je
1
01
s§
3
CO































s

BO
3 *•
VJ -rf
I* 2
g"
fid



X








X






















OPERATIONAL NOTES





Temperature, 95°
Recycle pump off, 1 hrs.








Flow off NaOH, ? hrs.

Recycle pumps off, ? hrs.











recycle pump off, ? hrs.




-------
              APPENDIX 8-2:  Page 4 Of  12



DATE








3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

21
22
23
24
25
26
27 ;
28
29 •.
BIOLOGICAL REACTOR
Influent
Flow Rates
gpn

jj
tj c
C 3


U












1












1
-




I*
«
S









1

1







1











CHEMICAL ADDITIVES
Daily Dosage
Pounds

§v
u
"c *
g 3
E tn








16
24
24
24
20





24
24

24
24
24
24
24
8




C
o

E

, ]





























0)
3


c
3
co






























_
 E
0 -
u c
S S
X
o












68




3.0
3.1

3.1
4.6
3.0
5.3

3.1

3.1
3.1


i „
O tt*
4J
l*J -rt
.gS
E S



12.0

15.0

15.0
11.0

1.5

7.5
11.0
7.0
3.0

5.0
5.0
3.5

3.5
4.5
4.0

4.0
3.5
5.0
5.5
4.5



^^

«.





570

510

610


280

350

428


70

90


200








M
.s
-
s
^
r?
U
01 01
vi tn



3 1/2
31/2
6
5
4
4 1/2

4 1/2
7
4 1/2
5
6
7
5
5
4
6 1/2
9

11
15
11

6
10

4
4
Return
Sludge


cj w
H4 -rt
u* ~*
O ^
$ 6




25.0

25.0

19.0


10.2

15.0

17.0
6.5

7.0

7.0


20.0


4.5

8.0

16.0
tn
•a
Z*
en
•a
-S ^
C M
o) e
3































Special
Conditions
^
u
i
00
c
g
«
r?
Si


X
X


X




X

X
















00
e
3
co

on
•o
J2








X






















(U
-5?
^
» t
-rt IB

0) U
£



































OPERATIONAL NOTES











Out of T.B.P.





Intermittent caustic addition




Recy cle pump of f , 1 hrs .

Power off, 40 min, emergency air
on
In t e rmi 1 1 en t c-aus tic addition
Intermittent caustic addition







Ol

-------
              APPENDIX B-2:   page 5 of 12



DATE



30
31
6-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
BIOLOGICAL REACTOR
Influent
low Rates
gpm

iarbonacec
Unit
Effluent


































»4
V
$




1




























CHEMICAL ADDITIVES
Daily Dosage
Pounds

Anno ni am
Sulfate




24
24
24
12
12
12
12
12
12
12
16
8
8
12
12
20
24
24
24
24
24
24
24
24
24
24
24
24
24

Limestone

































%
~S
»j
u
c
V


































Hydrated
Line


































Sodium
Carbonate






4
2
2
2



2
4
3
3
2
4
2
2
2
2
2
2
2
2
2
2
2
2
2
2
llHHters
u
Phoaphori
Acid




150
150
150
200
200
200
2OO
200
200
200





2OO
2OO
200
20O
200
200
200
200
200
200
20O
200
200
2OO

Trlbuytl
Phosphate

































Sodium Hydroxide
Peed Solution
Volumetric
Composition
X
O '
Se
g
U*l

















40OO


7000
9000
1500
9OOO
1500
12000
1000
10000
2000
13OOO
15000

M •
W ~*
.3


















40


40
40

20

40

40

40
40


V
!l
£ •














Yes
Yes
Yes
None
50
Yes
Yes
100
100
100
50
75
75

75
75
90
100

HIXED LIQUOR

b.
«
T3
u
a
t.
V
!

93
90

89
85
87
90
87
92
92
91
91
93
95
95
95
96
95
96
93
93
95
95
95
97
94
95
93
94
95
96
95



s

8.0
8.0

7.8
7.9
8.3
7.9
7.6
8.0
8.7
8.1
7.9
7.6
7.4
7.4
6.8
7.1
6.5
6.9
6.5
7.4
7.1
7.0
6.4
6.7
7.2
7.1
6.7
6.9
7.2
7.4
7.8


>. C"l
Alkalinlt
mg/1 CaCC

290
350

190
175
240
240
2OO
2OO
225
2OO
170
103
112
83
35
80
25
37
50
83
- 33
48
20
45
77
100
45
1OO
90
105
66

c?
•o -••.
* »
> £
1 c
m tt
s!

3.1
3.1

3.0

3.0
2











2.0
3.0
2.4
2.9


3.2
3.0
3.3
2.9
2.9

2.3
3.7


w
c
Imhoff Cc
ml/lltei

6.0
7.0

5.0
4.0

2.5

2.0
1.6

1.2
1.4
1.7
1.5
5.0
2.0
3.5
2.0
2.0
2.0


1.5
2.5
1.75

2.0


2.5


n
^
^
o ,
V)
•o
•o-—
|r
9
cn


































il

-------
              APPENDIX B-2:   page 6 of 12



DATE




7-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
BIOLOGICAL REACTOR
Influent
Flow Rates
gpm

i
h!
j> = C
3 S






1/4














1/2











V
3






3/4














1/2






1


CHEMICAL ADDITIVES
Daily Dosage
Pounds


1 2
E u)
24
24
24
24
24
24
24





















16
16
12


C
o
e
































 fc
1 =
tfk V)
Q S
2.4
2.7
2.5


3.1
1.8
2.1
2.0
2.4
2.0
2.9
3.1
2.3
2.7

2.6


2.3
2.7
2.9
2.1
3.0
3.6
3.3

2.9

3.5
3.1




-------
APPENDIX >-2:~ page 7 of  12
.


DATE






8-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
BIOlOCICAl REACTOR
Influent
Flow Rates
gpm

u
0 =

u




















0.25










a
fQ
^









0.9

0.88








0.7








CHEMICAL ADDITIVES
Daily Dosage
Pounds

E V
-3 «
O —i
j*

12
12
12
12
12
12
12
12
12
12
12
8
8
12
12
12
12
12
12










c
o
«

-5































>j
c
3
oa






























•o
01
Qt Ol

|3






























2
§ §
TJ .0
0 t.
U

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2

2
2
2
2
2
2
2
2
illlliters
u
^
: -o
o. *•
at u
3 <

200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200











-* tJ
J 0)
3 Q.

rl O
-i B.





























Sodium Hydroxide
Feed Solution
Volumetric
Composition

1-
ya E

in




5000
























kl •
0) •-<
« 00





40
























2
tf C
Tj •£
Ol r*

None
None
None
Yes
35



None
None
None

None

None



125
Yes
None
None

None




MIXED LIQUOR

k.
a
»*
^
IB
^
H

96
97
97
97
96
95
95
95
95
95
98
93
94
97
98
96
96
96
90
94
98
98
98
96
94
92
94
92




X
p.


8.0
7.7
7.4
6.9
6.8
6.4
6.8
6.7
6.7
6.6
6.5

7.0
6.7
6.6
6.7
6.6
6.6
6.4
6.3
8.7
8.5
8.4
8.6
8.2
8.0
7.8
7.8


>> £»
u O
"-1 U
T* O
01 ,-1
5 t

175
120
80
50
43
24
75
45
45
20
55

78
30
40
15
20
15
75
20
420
245
205
200
275
205
265
150

r-j
O
TJ -*.
S V
> 1=
1 5
-*J 00
Ql

3.3
2.9
3.0
4.0

3.1









1.8
1.2
1.8
2.2

1.8
2.1
2.2
1.6


2.7
2.6


V
e
3 S
*j
o *^
.E r-t
M ^



2.5

2.5

2.1


2.0

5.2

1.2


1.2

1.0

2.0


0.9
1.0
1.25

2.5
-o
•H
£
X)
•O ^^
C 00
1

3
in






























*!
o
-
§
ft
o
o

to

8
8
10


12
11
13
13
3
10
10
10
3
12
14
14
15
31
29
5
4
4
6

7
7
6
Return
Sludge




c
O M
O a
iw ^j
IS

M



5.0

5.0

5.5


3.0

5.2

3.3


2.0

3.5

209.0


2.1
3.0
2.5

2.0

•o
-
V)
•o C
C tf)
s. *
ta
VI





























Special
Conditions

^
o
u
J
W)
•-
0
£
































i
Of
00
tJ
3
to






























01
00
13
3 *•<
e S
iH 
-------
                APPENDIX B-2:  page 8  of 12



DATE




29
30
31
9-1
2
3
4
5-
6
7
8
9
1O
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
BIOLOGICAL REACTOR
Influent
Flow Rates
gpm

•
3
8 w
1 Carbonac
Unit
Effluen
O
0
0
0.25





0.25
v
























u
o
u

































Daily Dosage
Pounds


E «
Amnoniu
'" Sulfat


































S
S
I

































S
€
-J
S
m


































•0
01
II
x"^


































4)
1 Sodium
| Carbona
2
2
2
2

2
2
2
2
2
2
2
2
2
2
2
2
2
2

2
2
2
2
2

2
2
2
2
2
2
MlUiliters

u
b
Is
r


































4J
Trlbuyt
Phospha



















20




20

20
20
20
20
20

Sodium Hydroxide
Peed Solution
Volumetric
Composition

X
O -
st
g
in




60OO
90OO
12OOO
750O
9000
6OOO
6000
9000
9OOO
9OOO
9000
9OOO
900O
9000
9000
9000
9OOO
9000
9000
10000
10OOO

10OOO
10OOO
10OOO
10000
10000
9OOO

tJ -
« ~d
4J (g
.-




40
40
40

40

40
40
40
40
40
40
40
40
40
40
40
40
40
40
40

40
40
40
40
40
40


V
u
2 |
•o ---
I •

None
None

120
125
50
35
125

160
125
150
155
160
155
155

140
140
135
150
150
155
155

140
150
160
155
150
150
HIKED LIQUOR

b.
*
• u
V.
3
w
i
|
93
94
95
93
90
94
95
94
94
97
93
93
95
94
94
94
95
97
93
98
95
96
97
94
95

92
95
93
90
84
85





3:
a.
7.3
6.7
6.7
6.5
6.1
6.7
7.0
6.8
6.3
8.3
7.0
6.6
7.0
7.2
7.3
7.2
7.3
7.4
7.5
7.2
6.9
6.9
6.9
7.0
7.0

7.8
7.0
7.0
7.0
7.1
7.5




4J Q
•M U
5 3
S Z.
3 S
80
30
20
25
45
45
65
40
35
195
60
50
80
90
88
88
125
115
165
9O
72
80
8O
90
80

165
80
80
80
80
130

o
;
•o *^
s »
> £
.-<
i Disso
1 Oxygen,
3.5
1.3
1.0
3.0

1.9
2.2
2.9

1.4
1.8
2.2
2.2
2.0
2.3

2.1
2.8
2.4

2.2
2.3
2.7













-------
              APPENDIX B-2:   page 9 of 12




DATE







30
10-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
BIOLOGICAL, REACTOR

Influent
low Rates
gpm

u


C 3
In
HI

































li
% fi
« S

ft (J

M ' — .

180
110
70
60
45
65
65
140
80
55
50
40
55
40
47
57
45
43
55
50
130
185
520
65
75
90
130
80
57
111
LIQUOR

o"
-o —
.*
O "
u) c

S S
S




2.6
2.2
2.1

2.7



4.1
2.8
2.4


2.7

3.1


30
3.8




3.7
2.8
2.4


S
(S V
w

1*4 ~4
O ^


20.0

10.0


20.0
11.0
30.0
23.0
24.0


25.0

15.0

15.5


15.5
35.0
13.0
25.0
10.0

12.0
10.5
10.0
13.0




^
op
E



































H
H
C
°
u
a
u


"5
u>

6
5
5
4

4
6
6
6


8
5
6

6
6
6
6
6
6


7
7 I/:
7
6
6
6
6
Return
Sludge




o u
u e
lu ii


"E ~e
"

26

26


25

60

10


30

30

50


40.0

24.0

20.0


2.5

35.0


"D
Z!
•o
•o •--
C M
» e
a.
09
3
m































Special

Condlt Ions

h
o
1
Sf
c

g
^
































00
f?
i
QJ


3
U)
































01
00
•o
- s
W) t*
•5 «
U -J
« U
O
b*




































OPERATIONAL NOTES






Waste feed off, ? hrs.
Waste feed off, ? hrs.
Waste feed off, ? hrs.


















Note high ph caused by low Ph 0






Inte rmittent caust ic

Ui
VO

-------
APPBHDIX B-2:    page 10 of 12



DATE


30
31
11-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
2O
21
22
23
24
25
26
27
28
29
30

Influent
Flow Rates
SP"
1 .
1 Carbonic
Unit
1 Ef f lu»n

































0
































BIOLOGICAL REACTOR
CHEMICAL ADDITIVES
Daily- Dosage
Founds
E •
3 u
E en
6
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
12
12
8
12
12
12
12
12
f
9
12
12
12
12
12
tt
c
Limtito
































*
c
on
































-o
u
































„
Sodium
Carbona
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Kiililiters
o
f1
































-_« AJ
1 Trlbuyt!
Phoiphai
































Sodium Hydroxide
Feed Solution
Volinsetric
Composition

50% NaOH
ml.
9000
12000
135OO
13500





3000

3000
3000
3000
30OO
3000
3000
3000
20OO
3000
450O
5OOO
7OOO
9OOO
9OOO
9OOO

3000
60OO
7500
12000
7OOO

I8
45
40
40
40





50

40
40
4O
40
40


30
40
40
40
45
45
45
45

22
4O

40
45
V
a C
1 •


110
115
None
None



100

100
100
100
80
8O


150
150
125
150
150
150
150
150
None
100
75
75
75
ISO


b.
|
V
81
80
83
83
76
77
76
76
83
88
86
81
82
81
83
82
77
74
SO
83
85
83
83
88
83
73
75
85
80
87
89
83



3:
a
7.3
6.7
6.7
6.9
9.4
8.8
8.4
8.1
7.5
7.O
6.8
7.O
7.0
7.1
7.0
7.1
7.1
7.4
7.O
6.8
6.6
6.7
6.8
6.8
7.1
7.7
6.7
6.9
6.8
6.5
6.7
7.0


^8
C •*
-v* O
« «-•
Jf ""»•
167
55
55
63
960
565
380
225
110
55
50
65
58
67
55
47
63
97
6O
50
33
37
4O
42
65
17O
35
47
37
27
37
70

o
•s"
Dl»o
Oxygen,
2.4

2.0
2.6
7.2
3.8
3.9
3.4
3.4

3.3
3.9
3.1

4.5

2.8
3.7
2.9
3.1
2.4
3.2
2.9
2.8

3.2

3.1

3.6
3.0
3.4


O »*
1
20.O












5.0



5.0
5.O
4.5
4.O
4.5
5.0

5.0

4.0
4.O
3.0
5.3

4.5


_,
?

































•sl
TJ
e
w •
2S
c
V •*«
e.c
ta m
7
8
8
7
8
7
5
8
7
8

8
8 1/2
7
9
9
9
7
7
7
8
9
9
10

1O
1O
10
10
9
9
9
Return
Sludge



Is
It* VJ
O "•••
£ ^
15.5


10.0
18.0
15.0




5.5

5.5
10.0
8.3


8.0

5.6

5.4


1O.O

10.0

5.2


10.0



rt.
£
































Special
Con** *•"*•""*

^
o
1
I




X






























3
1
in
1
































V
«D
jj jj
»s
|3




































OPERATIONAL NOTES
























Waste feed off, ? hrs.
Waste feed off, ? hrs.
Waste feed off, ? hrs.





Aerator off, 1 hrs.

-------
APPENDIX 1-2:    page 11 of  12



DATE

12-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
BIOLOGICAL REACTOR
Influent
low Bates
gpm
Carbonaceous
Unit
Effluent



























M
V
S



























CHEMICAL ADDITIVES
Daily Dosage
Pounds
Amnonium
Sulfate
12
12
12
12
12
12
12
12
3










.







Limestone



























1
4t
a
IK



























Hydrated
Lime



























Sodium
Carbonate
2
2
2
2
2
2
2
2

2
2
2
2
2
2
2

2
2
2
2
2
2
2
2
2
2
llliliters
Phosphoric
Acid



























Tribuytl
Phosphate



























Sodium Hydroxide
Feed Solution
Volumetric
Composition
5O7. NaOH
ml.
8000
10000
10000
10000
12000
10000
1OOOO
10500
11000
11000
11000
3000
7000
7500
7000
7000


3000
3000
4OOO
7500
9500
9500
75OO
8500
9000
•4 .
V —
ss
45
45
45
45
40
40
40
45
45
40
40
40
45
45
40
40


45
45
45
45
45
45
60
50
45
ai
*j
fl
£*
150
150
150
120
125
140
140
150
150
150
13O
130
150
150
150
150


150
150
. 150
150
150
160
180'
150
150
MIXED LIQUOR

b.
Temperature *
88
9O
91
88
87
88
81
84
86
86
88
78
78
78
81
84

83
88
SS
88
84
88
80
82
75
78


£
6.8
6.8
7.0
6.7
6.8
6.9
7.2
6.8
6.8
6.9
6.9
6.4
6.8
6.9
7.2
6.9

9.4
6.9
6.8
6.8
6.8
6.8
7.4
7.1
7.7
7.1


Alkalinity,
1 mg/1 CaCOj
45
43
65
50
53
57
102
57
57
70
75
190
57
65
88
60

500
52
47
47
50
47
120
80
167
78

(M
O
Dissolved
Oxygen, nig/1
2.8
3.0
1.8

3.1
2.9
2.5
4.8
4.6

2.5
2.7
, 2.7

3.0
3.0

2.9
3.3
3.0
3.0
2.4
2.8

2.9
2.8
2.9


Imhoff Cone
ml/liter
4.0
4.5
2.5
4.0
4.2

4.5

5.5

5.5


5.5
4.0
4.0

4.0
3.5
4.5
4.0
5.5
3.5

4.5
5.5

in
•O
Z3
Suspended Sc
mgA










220


480
370
160












Z£
g*
1.:
Sedlmentat'
Secchi Dlsi
9
19
20
12
13
11
11
17
15
11
11
10
8
8
10
10

10
10
10
9
9
9
9
10
9
9
Return
Sludge



u
Imhoff Com
ml /liter

17.0

5.5


5.2

10.0

8.0


8.0

5.0

4.5


5.0

8.0

10.0



10
•0
A
Suspended S<
mg/1



























Special
Conditions

i«
o
(j
I
1





























-^
jt
1
w
3
V)




























9
00
1 >.
Floating SI
Clarlfl<































OPERATIONAL NOTES




Waste feed off, ? hrs.
Recycle pump off, ? hrs.
Waste feed off, ? hrs.






Waste feed off, ? hrs.

Waste feed off, 6 1/2 hrs.

Waste feed off, ? hrs.




Sludge return problem
Waste feed off, ? hrs.




-------
             APPENDIX B-2:  page  12  of 12



DATE




28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
12
13
• 14
15
16
17
18
BIOLOGICAL REACTOR
Influent
Plow Rates
gpm
A
S *j
O p 1-4
t £
o





















-


s























, CHEMICAL ADDITIVES
DaLly Dosage
Pounds

12
i "3
!«























s
i
s
J






















s
B
c
3,























-0
S I
£-•























flj
i s
? E
"3
2
2
2
2
1



1
2
2
2
2
2
2
2
2
2
2
2
2
2
Milliliters
w
s

e '























QJ
>v J^
3 a.
££






















Sodium Hydroxide
Feed Solution
Volumetric
Composition
3.
Si
g
9500
10000
10000
60OO
6000
7000
9000
8000
6OOO






3000

4000
4000
4000
5000
6OOO

B-
a to
45
45
45
4S
45
40
45
45
40






40

50
40
40
45
45

at
,3 c
E
•o **.
1 =
150
150
150
150
150
145
150
125
145


None



130

150
150
150
150
150
MIXED LIQUOR

Ft.
01
w
H
H
83
86
83
80
78
80
86
82
76
74
74
74
75
83
84
85
91
92
91
85
84
84




£

6.9
7.2
7.0
7.2
6.9
6.9
6.7
7.1
7.0
7.1
6.7
7.3
8.0
8.0
7.4
7.4
7.0
7.0
7.2
7.1
7.3
7.2


£ -
1 I
•** O
ttt — 1
S "i
58
75
85
98
53
53
45
80
80
80
40
90
225
205
77
125
25
70
83
70
85
70

o"
<<=
O -
3 S
g
2.6
2.6
2.9
2.4

2.9



2.4


2.8
3.7










ei
C
5 S
O --
3^
7.0
5.5
6.8
7.0'
5.5

4.5
5.0
5.5
5.0

4.5


3.0
4.5
4.5
5.0
5.0


4.5
•o
'£
-o
1^.
10
in























ll
H j:
c
0 -
n TJ
0) t4
e £
TJ y
01 (1)

9
8
10

9
10
10
9

8
7
7
6
4
6
2
8
21/2
7
6
7
6 1/2
Return
S LodKe




ss
ss
jj-i

8.0

9.0

6.1


29.0

8.0

5.0


8.0
8.5
7.5

5.5


7.0

•o
£
•o
C WD
o. B
(a
CO






















Special
Conditions



























«



' c?-
1
4)
00
•c
VI























V
00
1 s
c ~*
i 3
0



























OPERATIOSAL NOTES
























-
o\
to

-------
                                                APPENDIX B-3:
                                                               BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES
                                                                   Analytical and Operational Data for the Denltrificatlon Unit


DATE





2-1-70

2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26

27
28
3-1
2
3
4
5
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm

Jj
(U
< *J 3
f* *JLJ
; °u
z
1




































w
ft)
5




































Additives ,
Working Solutions


• n
fl) C
M a.

4.6



2.3





























3.5
 (U
to to







5
4 1/4
3 1/2
3 1/4
5
3 1/2
3

3
3
2 1/2
2 1/2
3 3/4
5
7
5
4 1/2
4
4
3
3 1/2

4
3 1/4
31/2
3 1/2

4
4
RETURN
SLUDGE

4
•*
"5
4-4 ^4
O "^-
•§ B
M





30.0

40.0


40.0

40.0
40.0
40.0
40. 0
40.0
40.0

40.0

40.0

40.0
40.0

40.0


40.0


15.0

13.0
9.0



•O U)
C -D

to o
3 to
to




































SPECIAL
CONDITIONS



op w
-.4 *J
E u
g 3







































. g
00 -H
*O Ji
S 3




































0)
44
oo a
B -4
a at
£ IS
to



















X








X









OPERATIONAL NOTES




Added 20 Ibs. of sewage sludge to
reactor sludge recycle 1 gpm.

Recycle pump problem
Sugar concen trat ion reduced





















2% blow down initiated, to cont. on daily
basis
-
Recycle pump off, ? hrs. Flow off, ? hrs.

Flow off, ? hrs.


Increased B.O.D. feed by 50%
co

-------
APPENDIX B-3:  page  2 of  10


DATE









6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21

22
23
24
25
26
27
28
29
30
31 -
4-1
2
3

4
5 ;';"
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
Q
-r-l 4J
nl flj
• i
U AJ 3
tLj 'ri llj
**j ^ *^
* w
.
z





































w
QJ
4-*
J



































Additives,
Working Solutions



•« «i
M n3
a c
00 j3
(A P-










'





















'


U)
01 tt)
at .u
W .H
CO i-l
(d 1-1
1— 1 !— 1
o •-<
S 'rf
E





















- .















« •
U ta
(U ^

CO 00
3




































V

M .
PQ C
•H
•Q E
"^
[14 £


































Mixed Liquor
Ft
 e
•— i
O "
ca d
CO ,
O






























	 —•
••- 0 ft
...


W "*».
O «-•
js e
&


6.0

2.6
2.0

1.5




4.0

5.0

1.3



.8

1.0

2.0


2,5

5.0

6.5



3
o
Efl
13 ^-*
01 —
•O Ml
d E
(U
Q,
CO
3
OT



































^ 0}
C J2
(0 U
H C
O "
•U to
to TJ
4J Q
C

E J3
•H O
•O o
Q) 
-------
              APPENDIX B-3:
                               page 3 of 10


DATE








6
7
8

9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28

29
30
5-1
2
3
4
5
6
7
8
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
c
Q
11 4J
it C
Is ji

*j J? »Tj
*]j r»1
M ix4
••j
ja





































n
2
*^
•S
**





































Additives,
Working Solutions


u«
ca c
M P
3 O
CO O-





































(0
in QJ
(U u
in -H
w »-•
cd ^
r-i ^j
o ^
S *^
g






































i-i M
<1) i-H
kJ ffl
d 60







































u
g c
•r-4
13 €
D *••*„
y ^^
^ €




































Mixed Liquor
ft.
0)
a
(0
 e
PH
O -
CO C
V) Q
*^ &0.
Q ^\
M
0












r-
























cu
o v
O 4J
JJd
O r-*
J= E

^3


20.0

14.0


1.25


2.0

3.0

.05


1.25

2.5

2.0


4.0


2.5

.5


.3

2.5

2.5
UJ
•X)
•l-l
o
CO
•a ^
It
V
a.
tn
D
en























220


200

240


210

180

240

w
e
(0
H
C
•H
m
d
1
^^
*O
Q)
en en


2 1/2

4


9


4
4
4
3
3 1/2
3 1/2
3
4
3
3
3
3 1/2
3
3
3 1/2
3 1/2

3 1/2

3
3
3
2
3
3
2
3
RETURN
SLUDGE

*i
01
c
0 n ,
iw £'
4-1 v-t
O ^"^
rC •""*
£ £
1*4

35.0

26.0


2.50


2.0

2.0

3.0


1.5

3.0

7.0


7.5


1.5

1.0


.5

3-5

3.0

op
B
TJ
~C %
0> -H
a. —i
en o
3 en
en




































SPECIAL
CONDITIONS


CO M
0 0
^ u

O flJ
fTT| p^




X


































00
m (Jj
60 i-l
•a ^
•3 ^*^
T— ( ^
to ffl





































a
S
60 «
e .-i
« °
rt v
O 00
•-I *O
fa 3
^^
cn









X

X


























OPERATIONAL NOTES









Rising sludge noted during Imhoff cone
test








Recycle pump off, ? hrs.

Recycle pump off, ? hrs.
Molasses feed off, ? hrs.







Sludge recycle, 1 gpm; losing solids from
clarifier







ncr eased molasses from 1500 ml to 3000 ml


Ul

-------
APPENDIX B-3:  page 4 of 10


DATE







9
10
11
12
13
14
15
16
17
18
19
20
21
22
23

24
25
26
27
28
29
30
31
6-1
2
3
4
5
6
7
8
9
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm

4-1
G
< 01
4J 3
IS
vu

z
































-



**
01
3

























;









Additives,
Working Solutions


A (Q
kt "O
4 C
10 a



































10
4 0


































Mixed Liquor
h
0)
3
td
K

H

86
88
90
91
88
87
88
84
80
84
86
87
87
86
88

85
86
90
84
89
87
91
86

85
82
84
84
85
86
88
88
CM
O
r-t
> e
o »
m C
w at
SK
X
o












.1

.2




.2




.1

.2








a" n
o w
CJ 4J
1^4 ^^|
1-1 "^
|1
M




5.2

6.0
.031
6.0


3.5

3.5

1.5
5.0


2.0
3.0

2.5
5.5
3.5



4.5

1.0

.7
.7



-
do
E






210

110

140


60

110

80




















Tl
C
O *
u o)
C
V -H

•*4 -0
"O U
l> a>
CO CO



3
4
4 1/2
3
2 1/2
3
4
3
3
3
3
4
3 1/2
31/2


4
4 1/2


2
3
3

2 1/2
2 1/2
1 1/2
3
2
2
2
2
RETURN
SLUDGE

•
c
O M
U Hi
4J
•W **4
o *-.
€ E
H



2.0

1.0

11.0


4.5

5.5

1.5



2.0



13.0

3.0


15.0

2.5


.6



•o
0) *
-a a,
c -o
O. ~<
a o
3 en
OT


































SPECIAL
CONDITIONS


60 14
C O

H t)
g 8
fe fid





































bO
at c
DO -H
3 r-4
^ d
vi pa



































M
o>
S
14
g-5
•* cj

<0 at
E'I 3
— ^
la














X





















OPERATIONAL DOTES











Baffle installed in clarifier
Floating solids




Power off 4O min.


Skimmer installed on clarifier; sludge
recycle, 1/2 gpm.



Recycle pump off, ? hrs.



-
Bad odor
Normal operation

Dark color, bad odor




Recycle pump off, ? hrs.

-------
APPENDIX B-3:   page 5 of 10


DATE


10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
7-1
2
3
4
5
.6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
BIOLOGICAL REAC.TOR
Influent '.
Flow Rates,
gpm

:riftcaUc
Unit
Effluent.
z










































Water










































Additives,
Working Solutions •

- to
I- T3
(0 C
do 3
3 O-
w (X










































«
Molasses,
illiliter
£










































U tn
Q> _t
U (0
SM











































o
u
Sc
*$
o> — •
b E









































Mixed Liquor
CM
«
0)
emperatur
H
88
90
91
93
92
92
92
92
92
90
92
92
92
93
90
91
90
93
92
93
93
91
93
92
92
92
90
92
91
91
95
92
93
91
91
91
93
92
92
92
91
cf
!~l
^ "^ ;
Dissolve
xygen, mg
o







.1
3.0




.2
1.0

.5






1.3


..
.2
.2
.2




.2
.2






8\
Imhoff Co
ml/lite

.8
.7
.7

.4
.3
.5
1.0
2.0
1.0


.5
1.0
.7

.5


.5

1.0




1.0

1.25

.2


.3

.5

1.0


1.0
(O
•o
•r-J
O ,
CO
•a -*
01 -*.
1 %
a.
U)
3
O3










































.M fl
1
c
O "
•H
ij
Sedimenta
Secchi Di

2 -
1 1/2


2 1/2
2 1/2
3 1/2
4
5
4
4
3
3
3
4
31/2
4
4
3
4
4 1/2
3 1/2
4
4
4
4
4
3
3
3
4
4
3

4
4
3
3
3
3
3
RETURN
SLUDGE

u
mhoff Con
ml/liter
HI
3.0

1.1


.8

5.5

6.5




2.0








.7


2.5



1.0


.5

1.0

2.0


1.2
^
' 	
00 .
uspended
Solids, in
CO









































SPECIAL
CONDITIONS


Foami ng
Reactor












































Sludge
Bulking










































Vf
0)
•H
*M
i-l
Floating
udge Clar
.— i
CO







































X




OPERATIONAL NOTES











































-------
             APPENDIX B-3:  page 6 of  10


DATE




21
22
23
24
25
26
27
28
29
30
31
8-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpro
c
O
i-i JJ
T* Jji
Q V
O 4J 3
fl •*< i-4
«M C M4
•H » «W
H H
4J
•v4









































s
5






































Additives,
Working Solutions



si
!?§
en a






































to
•« Vi
SO)
.u
CO vi
r-< **
O i-4




















3000
3000
3000


3000
3000
3000
3000



3000
3000
3000
3000





 f
^4
0 -
to e
(0 41
•H 00
°l

.2

3.1
.4
.2
.7




.02


















.7








0)
C M
O 01
U «J

p


1.0

1.0




6.0

3.0


2.0

10.0

1.3


.5

6.0

1.0


.3

1.0

15.2


5.0
3.5
3.0
3

_,
^i^
,f







































H C
•H
e
o *
•H U
4J to
a -H
4J O
e
Sedime
Secchi

4
3
3 1/2
3
4
4

3
2 1/2
3 1/2
4
4
4
4


4
4
4
4
4
4
4
4
4
4
5
4
3
10
13
2
2
2
2

3 1/2
RETURN
SLUDGE

w
e
O b
O V
4J
M-l v4
o •*-.
3 -a


2.5

3.0




7.5

4.0




20.0

1.2


.6

1.0

20.0


.3

2.5

70.0


20.2
15.3
11.0

•^
•0
ty •»
C TJ
O. r-4
(a O
3 en






































SPECIAL
CONDITIONS



tiQ I*
"s o
1 1









































00
V C
tlO -H
•o ^
y -•
en pa


X



































5
5
00 «
e -4
nj a)
CO











X




























OPERATIONAL NOTES












Waste flow off, ? hrs.


















Molasses pump off, 4 hrs.
Intermittent flow rate of molasses





;Bad odor

00

-------
               APPENDIX B-3:   page 7 of 1O


DATE



27
28
29
30
31
9-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
10-1
2
3
4
5
6
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpro
a
A
:rificatic
Unit
E-f'fluent
,
2










































U
V
$











































Additives,
Working Solutions

- en
(0 C
00 3
3 0
to a











































(0
Molasses,
IHiliter
g




3000
3OOO






3008






























0) -4
l^












































V
£<:•
"1
I£'E




150
150






150





























Mixed Liquor
h
•h
emperatur
E-t

89
88
90
90
9O
90
87
92
93
92
98 .-5
92
92
93
93
92-
92
92
92
93

94
92
93
94
92
94

89
92
90
87
82
83
85
84
86
88
89
90
92
0N
13 -•*
Dissolve
xygen, mg
o






.1






1.0

1.0



























0)
C h
33
J 1



2.5


2.0

2.0

2.5


0.2

3.5

1.0


1.5

5.0

5.5


9.5



2.5


3

4.5

3


4

CO
•o
O
VI
Tl ^
10
3












































M 1)
C
O **
•r4 U
4J «
Sedimenta
Secchi Di


2 1/2
3
3
3
- 3
3
2 1/2
- 3
. 3
3
3

3
2 1/2
3 1/2
3
3
6
3
3
2
3
3
2
2

2

2
2
3


2
2
2
2
2

2
2
RETURN
SLUDGE

Of
e
o »*
u s
«M -H
>t4 t-l
O ^
£ — * '
E e



3.0


5.4

6.0

4.5




11.0

4.0


2.5

10.0

10.0


20.5



20.0


15. 0

23.0

20.0


15.0


00
uspended
Solids, m
W)










































SPECIAL
CONDITIONS


Foaming
Reactor













































Sludge
Bulking






























X
X





X





•ft

M *
C ft
.-1 •«
fc 3
i— i
CO












































OPERATIONAL NOTES











































VO

-------
APPENDIX B-3:   page 8 of 10



DATE








7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
11-1
2
3
4
5
6
7
8
9
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11
12
13
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APPENDIX B-3:  page 9 of 10


DATE


15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1
2
3
4
5
6
7
8
9
10
11
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13
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16
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               APPENDIX B-3:   page 1O of 10


DATE





23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
12
13
14
15
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17
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                            APPENDIX^
Alkalinity is defined as  the  capacity  of  a water  to neutralize  acid.
For most waters, this ability can be expressed  by the  equation


Alkalinity, mg/1 CaCC>3 -  50,000(2[C03=] 4- [HC03~] +  [Olf] -  [H+])    (1)


where [  ] represents molar concentrations.   The  purpose of  the discussion
is to propose a reaction  scheme  for nitrification and  from this scheme
calculate potential  alkalinity requirements  for the process.  Verifica-
tion of the proposed chemical mechanisms  will be  attempted by making an
alkalinity balance on the system which includes,  in addition to the
biochemical reactions, the supplemental alkalinity intentionally added
to the system.  In order  to accomplish this  calculation, the sources and
changes in carbonate, bicarbonate, hydroxide, and hydrogen ions must be
known or estimated.

The principal reactions taking place within  the nitrification unit are
the oxidation of ammonia  to nitrite and nitrite to nitrate.  These two
reactions can be represented  by  the following equations:


            Nil,"*" + 2H20-»— NO ~ + 8H+ +  6e~                   .     (2)

and                                   ,
                            NO  + 2H  +  2e~                        (3)
As can be  seen,  these  reactions  produce hydrogen ions  which  are negative
alkalinity.   These  reactions  also produce electrons  (oxidation) and must
be accompanied by simultaneous reactions which utilize electrons  (reduc-
tion) .   Two  reductive  reactions  knox-m to occur during  nitrification in-
volve oxygen and the utilization of inorganic carbon by the  autotrophic
bacteria to  produce biological cell material.  The reduction of oxygen
is often represented chemically  as
             02  + 2H20 --9- 40H~ - 4e~



The reduction of inorganic carbon,  which in this case is present mostly
as bicarbonate, to  organic carbon is given by equation (5).,
                s

             HCO ~ + 3H  0  -*— CH 0 + 50H~ - 4e~                      (5)
                •J      ^        2,                     :
                                    173

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The hypothetical product, CI^O, was chosen because it closely approxi-
mates chemically the composition of cellular organic carbon.  Reactions
4 and 5 produce hydroxide ions which add to the alkalinity but bicarbonate
is used in reaction (5) which tends to lower it.

Test data is available which allows at best some approximation of  the
contribution of reactions (1), (2), and (4) to be made fairly directly.
Unfortunately no direct measure of the amount of oxygen utilized in  the
process was possible.  The amount of oxygen utilized can be made in-
directly through the use of an oxidation-reduction balance.  In other
words, the electrons released in reactions (2) and (3) and not utilized
by (5) will be assigned to reaction (4) , the reduction of oxygen.

To use an oxidation- re duct ion computation requires the assumption  that
all significant reactions are known.  This assumption is believed  to be
reasonably valid.  Oxidation-reduction balances are best made using  the
concentration units of equivalents per liter, epl.  From the data
available, nitrite production, according to reaction (2) , was best
estimated from the change in ammonia concentration through the unit.
Nitrite could not be used directly since the influent was not monitored
regularly for this constituent, and variable amounts may well have been
present.  In addition, some nitrite was converted on to nitrate within
the unit.  The equivalents per liter (epl) of nitrite produced within
the unit is given in equation (6) .
            epi(N02-N) = [CJCNH.J-N) - cE(NH3-N)]   14p00           (6)


where ,
            epl(NO~ -N) « equivalents per liter of nitrite nitrogen,

            Cj.CNH.j-N)   = influent NH3 as mg/1 - N, and

            C£(NH3-N)   - effluent NH3 as mg/1 - N.
The factors of 6 and 14000 are, respectively, the electrons released per
molecule of nitrite formed or equivalents per mole and the milligrams of
nitrite nitrogen per gram mole.

The equivalents of nitrate produced can be estimated directly from the
change in concentration of nitrate in the unit.  From the stoichiometry
of reaction (3) , this can be written as
            epl(N03N) - [CS(N03"-N) - C^NO^-N)]      QQ          (7)
                                   174

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The reduction of inorganicicarbon  according  to  equation  (5)  cannot be
evaluated from alkalinity measurements  for obvious reasons.  The alter-
native is to estimate  this  reduction  through the  increase  in organic
content of the effluent.  Two  alternate techniques were  utilized during
the test to monitor  this parameter.   During  the first phase  of  the ex-
periment, organic  Carbon measurements were made and  the  oxidation-reduc-
tion statement using organic carbon  (DC)  becomes
                       j

            epKHCO  ") =  [C (OC) - C  (OC)J	4_	                (8)
                                              12000

The second part of the test was monitored using chemical oxygen demand
and the statement  using this parameter  is


            epl(HCO  ~) -  [C (COD)  -  C (COD) ] 	  4	              (8a)
                                      X          32000

The use of either  of these  methods is not entirely  satisfactory as
undoubtable losses of  these materials occur  through normal aerobic
biochemical mechanisms and possibly  through  denitrification in  the unit
and its sedimentation  facility.

The oxygen  requirement can be  calculated using the  fact  that the equivalents
oxidized  must equal  equivalents reduced which is


            epl(oxidized)  = epl(reduced)                           (9)


            epl(N02~-N) + enl(N03~-N) = epl(HC03~)  + epl(02>        (10)
or
 Substituting and reducing equations (6), (7), and (8) gives the oxygen
 requirement in terms of mg/1 of 02

                  ') L               3         —       3  A
              2    7     ' * '3      7        3        3

 for those periods when organic carbon measurements were made and for
 those periods when chemical oxygen demand was used.


             02 = -j [AC(H!I3-N)] + -  [AC(N"03~-N)J - Ac(COD)      (lla)
                  •' 0 "
 where   C indicates the change in concentration
                                    175

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The numerical solutions for equations (11) and (lla) for those periods
of relatively good nitrification are given in Table C-l.  These  tabulated
results indicate the large amounts of oxygen required by the nitrification
unit.

This estimate of oxygen utilization now allows the computation of the
alkalinity changes that might be expected during nitrification.  Using
the definition of alkalinity, equation (1), and the stoichiometry of the
major assumed reactions given by equations (2), (3), (4), and (5), the
following equations can be derived for alkalinity changes in terms of
rag/1 CaCO :
(1)  Nitrite production -

            Alkalinity utilized - 50,000 [AC(NH.-N)]     8
                                                3     ~T4000~~

(2)  Nitrate production -

            Alkalinity utilized = 50,000 [Ac(NO ~-N) ] _ 2_ __   (13)
                                                4      "  14000
(3)  Inorganic carbon reduction -

     (a)  For organic carbon

            Alkalinity produced = 50,000 [Ac(OC)] _ 5_ _       (14)
                                                     12000
     (b)  For chemical oxygen demand
            Alkalinity produced - 50,000 [^(OC)] __  5 _       (14a)
                                                     3~2000
(4)  Oxygen utilization -

            Alkalinity produced = 50,000 [CO ] __ 4 _            (15)
                                                 32000

The results of each of these alkalinity changes is tabulated in Table C-l.
In addition, the algebraic summation of these changes is also given under
the column entitled total potential alkalinity utilized.  The require-
ment for alkalinity up to 4500 mg/1 must be satisfied or the process will
be self-limiting because of low pH and the lack of inorganic carbon.  The
alkalinity requirement to nitrify the entire waste stream would be very
large.   In the pilot plant, this alkalinity requirement was met by allowing
a decrease in alkalinity through the unit and by addition of soda ash
and sodium hydroxide.  The total of these alkalinity sources is given in
the table.

The difference between the calculated alkalinity  utilized,  and  the  alka-
linity accounted for by artificial additions and  changes in residual alka-
linity of the waste are also tabulated as both absolute amounts and as  a
                                   176

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                                   APPENDIX C





TABLE C-l:  Nitrification Unit. Alkalinity Balance for Selected Sampling Periods
Period









138-144
145-151
222-228
229-235
257-263
264-270
306-312
313-319
327-333
Ammonia
mg/1 N


4J
jj
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T—l
C
t-t
430
430
580
670
490
520
49O
41O
280


, ,
g

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W
120
50
330
380
50
130
110
80
50




U
1


310
380
250
290
440
39O
380
330
230
Nitrate
mg/1 N


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0
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C
1-4
O
0
0
0
0
0
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o
0


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-rf 0) o
c a. 
-------
percentage of the alkalinity utilized.   This  analysis  tends to show that
alkalinity changes could not be predicted  consistently using the reactions
involving the oxidation of ammonia to nitrite and nitrate,  the reduction
of oxygen, and the conversion of inorganic to organic  carbon and the
monitored data from the experiment.  Whether  these differences result from
assuming an inadequate chemical description of the process  or from inade-
quate data is not known.  In large measure, however, these  differences
may not be unreasonable considering  the  large multiplication factors
applied to a rather limited number of analyses on grab samples in the con-
version of these constituents to oxidation-reduction equivalents and to
alkalinity equivalents.  In addition, these potential  discrepancies are
magnified through two substractions  involved  in the computations.
                                    •'«     AU.S. GOVERNMENT PRINTING OFFICE: 1973 514-154/256 13

-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
       1. Report No.
                           w
   7/i     Biological Removal of Carbon and Nitrogen Compounds   5'. Deport Date
          from Coke Plant Wastes                                6.         .
                   ,                                             s.
   A  t-ior(s) -Barker, -John E.; Thompson, R., J.; Samples, w. R.;
          McMichael,  E.  C.
                       iron and Steel Institute
              150 East 42 Street
              New York City, New York 10017
                                                                   Report No.
                           10.  Pttijet.-t.ifi'

                             12010 EDY
                           11  Contract/Grant fie
                                                               \13.-~ Type t,.f Report and-
                                                                   Period Covered
     • p/eitienfary Note'
              Environmental Protection Agency report
              number, EPA-R2-73-167, April  1973.
16.  -4/i.s tract
         A  one-year study of a biological process for treatment  of  coke  plant ammonia
    liquor  was conducted.  The process was designed to remove  carbon  compounds and
    ammonia.   The pilot plant consisted of three treatment systems  arranged in series.
    These systems were designed for the removal of carbon compounds,  the oxidation
    of ammonia to nitrate (nitrification), and the reduction of  nitrate  to nitrogen
    gas (denitrification).   The study was jointly sponsored by the  American Iron and
    Steel Institute, the Environmental Protection Agency, and  Armco Steel Corporation.

         The  results of the study indicate that the biological process can be used
    to remove carbon compounds and ammonia from dilute ammonia liquor.   Treatment
    efficiencies obtained include removals of greater than 99.9  percent  phenol,
    80 percent COD, and 90 percent ammonia.  Removal efficiencies for cyanide and
    thiocyanate were less encouraging with averages of 57 and  17 percent, respectively.
    .(Myers  -  RSKERL)
17a. Descriptors
    Group 16 (VABC) Aerobic Conditions, Anaerobic Condition, Biochemical Oxygen
    Demand,  Heated Water, Industrial Wastes, Nitrogen Compounds,  Organic Matter,
    Phenols, Water Pollution Sources.


17b. Identifiers
    Coke Plant wastes, Ammonia Liquor, Nitrification, Denitrification,  Carbon Com-
    pound, Ammonia, Cyanide, thiocyanate, Phenol, State-of-the-Art,  Aeration Time,
    Problem areas, Sludge bulking, Activated Sludge, Pilot Plant.
17c. COWRR Field & Group
18. A \-ailability
39.'' ^Security das's.
•. . : :•• '(Report) . • ..' •
*fl. Security Cfrss,
. ' (P*JSe) •'• '
•21.' No. of
Pages
i 22. Ptiee
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 2O24O
          Leon H.  Myers
in* tiiuiioiRobert S. Kerr Environment i  Research Lab.

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